CN115739061A - Use of zirconium hydroxide as catalyst for preparing N-phenylformamide or its derivatives from aniline or its derivatives - Google Patents
Use of zirconium hydroxide as catalyst for preparing N-phenylformamide or its derivatives from aniline or its derivatives Download PDFInfo
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- aniline
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000001301 oxygen Substances 0.000 claims abstract description 71
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 146
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000001914 filtration Methods 0.000 claims description 32
- 239000007810 chemical reaction solvent Substances 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 7
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 5
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 5
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 5
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004442 acylamino group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 238000002360 preparation method Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 150000003754 zirconium Chemical class 0.000 abstract 1
- 238000001819 mass spectrum Methods 0.000 description 32
- 239000012298 atmosphere Substances 0.000 description 31
- 238000010438 heat treatment Methods 0.000 description 30
- 238000003756 stirring Methods 0.000 description 30
- 230000008859 change Effects 0.000 description 29
- 238000007056 transamidation reaction Methods 0.000 description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- -1 amide compounds Chemical class 0.000 description 3
- SXEVZVMJNXOXIJ-UHFFFAOYSA-N n-(4-methoxyphenyl)formamide Chemical compound COC1=CC=C(NC=O)C=C1 SXEVZVMJNXOXIJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LEBVLXFERQHONN-UHFFFAOYSA-N 1-butyl-N-(2,6-dimethylphenyl)piperidine-2-carboxamide Chemical compound CCCCN1CCCCC1C(=O)NC1=C(C)C=CC=C1C LEBVLXFERQHONN-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VVIAGPKUTFNRDU-UHFFFAOYSA-N 6S-folinic acid Natural products C1NC=2NC(N)=NC(=O)C=2N(C=O)C1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 VVIAGPKUTFNRDU-UHFFFAOYSA-N 0.000 description 1
- 239000004072 C09CA03 - Valsartan Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MPJKWIXIYCLVCU-UHFFFAOYSA-N Folinic acid Natural products NC1=NC2=C(N(C=O)C(CNc3ccc(cc3)C(=O)NC(CCC(=O)O)CC(=O)O)CN2)C(=O)N1 MPJKWIXIYCLVCU-UHFFFAOYSA-N 0.000 description 1
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 1
- BZKPWHYZMXOIDC-UHFFFAOYSA-N acetazolamide Chemical compound CC(=O)NC1=NN=C(S(N)(=O)=O)S1 BZKPWHYZMXOIDC-UHFFFAOYSA-N 0.000 description 1
- 229960000571 acetazolamide Drugs 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 229960003150 bupivacaine Drugs 0.000 description 1
- FAKRSMQSSFJEIM-RQJHMYQMSA-N captopril Chemical compound SC[C@@H](C)C(=O)N1CCC[C@H]1C(O)=O FAKRSMQSSFJEIM-RQJHMYQMSA-N 0.000 description 1
- 229960000830 captopril Drugs 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229940121657 clinical drug Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HSUGRBWQSSZJOP-RTWAWAEBSA-N diltiazem Chemical compound C1=CC(OC)=CC=C1[C@H]1[C@@H](OC(C)=O)C(=O)N(CCN(C)C)C2=CC=CC=C2S1 HSUGRBWQSSZJOP-RTWAWAEBSA-N 0.000 description 1
- 229960004166 diltiazem Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VVIAGPKUTFNRDU-ABLWVSNPSA-N folinic acid Chemical compound C1NC=2NC(N)=NC(=O)C=2N(C=O)C1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 VVIAGPKUTFNRDU-ABLWVSNPSA-N 0.000 description 1
- 235000008191 folinic acid Nutrition 0.000 description 1
- 239000011672 folinic acid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229960001691 leucovorin Drugs 0.000 description 1
- 229960004194 lidocaine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- SJSNUMAYCRRIOM-QFIPXVFZSA-N valsartan Chemical compound C1=CC(CN(C(=O)CCCC)[C@@H](C(C)C)C(O)=O)=CC=C1C1=CC=CC=C1C1=NN=N[N]1 SJSNUMAYCRRIOM-QFIPXVFZSA-N 0.000 description 1
- 229960004699 valsartan Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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 belongs to the technical field of organic synthesis, and particularly relates to application of zirconium hydroxide as a catalyst in preparation of N-phenylformamide or derivatives thereof by using aniline or derivatives thereof. The invention discovers that the N-phenylformamide or the derivative thereof can be synthesized by taking aniline or the derivative thereof as a raw material, a zirconium hydroxide catalyst and oxygen as an oxidant through a catalytic oxidation reaction; the zirconium hydroxide catalyst can be purchased directly, or a zirconium salt precursor is used as a raw material, and the zirconium hydroxide catalyst is prepared by a simple precipitation method and has low price; the method has the advantages of simple operation, low production cost, high yield and easy industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an application of zirconium hydroxide as a catalyst to catalyze aniline or derivatives thereof to prepare N-phenylformamide or derivatives thereof.
Technical Field
Amide bonds are widely found in pharmaceutical intermediates (valsartan, captopril, diltiazem, lidocaine, bupivacaine, acetazolamide, folinic acid, glucosamine, etc.), pesticides, fuels, fragrances and natural products, and about 25% of known clinical drugs contain at least one amide bond. Traditionally, the construction of amide compounds has focused mainly on the acylation of amines such as acid chlorides, carboxylic acids, acid anhydrides, and esters. However, these methods have the disadvantage of low atom economy, mainly resulting in large amounts of waste, release of corrosive and volatile gases, experimental operationComplex, and poor stability of acyl halides. Meanwhile, most of these methods use a homogeneous catalyst, utilize formic acid and its derivatives and organometallic carbonyl compounds as formylating agents, and require strong acid (e.g., alCl) 3 Or SnCl 4 ) Or strong base (such as NaOH or NaOCH) 3 ) As a catalyst or additive to activate the amine or formylating agent. Furthermore, the addition of a homogeneous acid or base during the subsequent separation increases the difficulty of the separation.
Transamidation has in recent years become a simple and efficient method of establishing new C-N bonds. There have been many papers reporting the N-amidation of amines with N, N-disubstituted amides. Wangfeng et al developed a CeO 2 Catalysts, and show very high reactivity for transamidation reactions (see chem. Commun., 2014, vol. 50, no. 19, 2438-2441). The catalyst has wide substrate applicability, and does not need any additive in the reaction process. Akbar Heydari et al developed a superparamagnetic Fe (OH) loaded material 3 Fe (b) of 3 O 4 Nanoparticles for transamidation reactions (cf., RSC adv, 2016, vol. 6, 29, 24684-24689). The catalyst has the advantages of low cost, recoverability and environmental protection. Basudeb Basu et al further used metal-free Graphene Oxide (GO) nanoplates. The carboxylic acid groups present on the edges of the GO nanosheets act as active acid centers, activating weak electrophilic amide groups and promoting further attack of amine nucleophiles through hydrogen bonds. The reaction is carried out in the absence of solvent, and the catalyst can be recovered and reused more than three times (see Tetrahedron Lett, 2018, vol. 59, no. 10, 899-903). However, the conversion and selectivity of the above processes are desired to be improved.
Therefore, we considered a new approach, using a Zr (OH) 4 A catalyst for amide formation by double activation of amines and N, N-Dimethylformamide (DMF) at a relatively mild catalytic center with formation of new C-N bonds on a solid catalyst, which has excellent catalytic activity and selectivity.
Disclosure of Invention
The invention discovers that zirconium hydroxide or a composition containing zirconium hydroxide is used as a catalyst and can catalyze aniline and N, N-dimethylformamide to carry out transamidation reaction. Therefore, the invention provides a method for transamidating aniline and N, N-dimethylformamide under the catalysis of a zirconium hydroxide catalyst, and the method is simple, low in cost, high in safety and high in yield. The method specifically comprises the following steps:
in a first aspect, the present invention provides the use of zirconium hydroxide or a composition comprising zirconium hydroxide as a catalyst for the preparation of N-phenylformamide or a derivative thereof from aniline or a derivative thereof and N, N-dimethylformamide.
Preferably, the structural formula of the aniline or the derivative thereof is shown as the following formula (I), and the structural formula of the N-phenylformamide or the derivative thereof is shown as the following formula (II):
wherein R is 1 -R 5 Respectively selected from any one of hydrogen, halogen, hydroxyl, sulfonic group, nitro, substituted or unsubstituted straight chain or branched chain alkyl, alkoxy, carbonyl, alkenyl, alkynyl, substituted or unsubstituted aryl, acylamino and cyano.
Preferably, said R is 1 -R 5 Are respectively selected from hydrogen, methyl, chlorine, bromine and methoxyl.
Preferably, the aniline or derivative thereof comprises: aniline, o-methylaniline, m-methylaniline, p-chloroaniline, p-bromoaniline, p-methoxyaniline.
In a second aspect, the present invention provides a process for the preparation of N-phenylcarboxamide or a derivative thereof, said process comprising: aniline or derivatives thereof shown in the following formula (I) is used as a raw material, N-dimethylformamide is used as a reaction solvent, zirconium hydroxide or a composition containing zirconium hydroxide is used as a catalyst, and oxygen is used as an oxidant to perform catalytic oxidation reaction to synthesize N-phenylformamide or derivatives thereof shown in the following formula (II);
wherein R is 1 ~R 5 Each selected from any one of hydrogen, halogen, hydroxyl, sulfonic acid group, nitro group, substituted or unsubstituted straight or branched alkyl group, alkoxy group, carbonyl group, alkenyl group, alkynyl group, substituted or unsubstituted aryl group, acylamino group, cyano group, but not limited to the above substituents.
Preferably, said R is 1 ~R 5 Are respectively selected from hydrogen, methyl, chlorine, bromine and methoxyl.
Preferably, the aniline or derivative thereof comprises: aniline, o-methylaniline, m-methylaniline, p-chloroaniline, p-bromoaniline and p-methoxyaniline.
Preferably, the catalyst is used in a ratio to aniline or a derivative thereof of 1 to 1501 mol.
Preferably, the dosage ratio of the catalyst to the aniline or the derivative thereof is 10-100g.
Preferably, the dosage ratio of the catalyst to aniline or its derivative is 40-60g.
Preferably, the amount ratio of the catalyst to aniline or its derivative is 50g 1mol.
Preferably, the mass ratio of the reaction solvent to aniline or its derivative is 10 to 500.
Preferably, the mass ratio of the reaction solvent to aniline or its derivative is 100 to 400.
Preferably, the mass ratio of the reaction solvent to aniline or its derivative is 200 to 350.
Preferably, the mass ratio of the reaction solvent to aniline or its derivative is 300.
Preferably, the reaction solvent is N, N-dimethylformamide.
Preferably, the catalyst is zirconium hydroxide.
Preferably, the method comprises the steps of:
(1) Adding a zirconium hydroxide catalyst, aniline or a derivative thereof and N, N-dimethylformamide into a three-neck flask;
(2) Inserting a condenser tube on the three-mouth flask, inserting a balloon filled with oxygen into the mouth of the condenser tube, ensuring the whole system to be sealed, and reacting for 3 hours at 170 ℃;
(3) Filtering, distilling and recrystallizing to obtain the N-phenylformamide or the derivative thereof.
Preferably, the reaction temperature is 100 to 200 ℃.
Preferably, the reaction temperature is 170 ℃.
Preferably, the reaction time is 1 to 36 hours.
Preferably, the reaction time is 3h.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The zirconium hydroxide or the composition containing the zirconium hydroxide is used as the catalyst, so that the catalyst is low in commercial cost, high in activity and good in selectivity, can be directly purchased or prepared by a simple precipitation method, greatly reduces the preparation flow of the catalyst compared with the catalyst used in the traditional method, greatly reduces the cost of the catalyst, and is green and environment-friendly;
(2) The aniline or the derivative thereof used in the invention is a common basic raw material in industry, and is cheap and easy to obtain.
(3) The invention uses cheap and easily available oxygen as oxidant, and reacts under normal pressure, compared with the traditional method, the cost of the oxidant is greatly reduced, and the problems of toxic substance emission and production safety generated by using the oxidant are solved.
(4) The method can catalyze the transamidation reaction of aniline or derivatives thereof and N, N-dimethylformamide to generate the N-phenylformamide or derivatives thereof, the substrate applicability is good, and the yield of the target product is high.
Drawings
FIG. 1 mass spectrum of N-phenylformamide as the product of the synthesis of example 1;
FIG. 2 Mass spectrum of N-phenylformamide as a product of the synthesis of example 2;
FIG. 3 mass spectrum of N-phenylformamide as synthesized in example 3;
FIG. 4 mass spectrum of N-phenylformamide as synthesized in example 4;
FIG. 5 mass spectrum of N-phenylformamide as a product of the synthesis of example 5;
FIG. 6 is a mass spectrum of the N- (2-toluene) formamide product synthesized by the method described in example 6;
FIG. 7 is a mass spectrum of the product N- (3-toluene) formamide synthesized by the method described in example 6;
FIG. 8 is a mass spectrum of the N- (4-toluene) formamide product synthesized by the method described in example 6;
FIG. 9 is a mass spectrum of the N- (4-chlorobenzene) carboxamide synthesized according to the method described in example 6;
FIG. 10 is a mass spectrum of N- (4-bromobenzene) formamide as a product of the synthesis of example 6;
FIG. 11 is a mass spectrum of N-formyl-4-methoxyaniline as a synthesized product according to the method described in example 6;
Detailed Description
The present invention is described in further detail below with reference to specific examples, but the scope of the present invention is not limited thereto, and the raw materials used in the following examples are commercially available without specific description.
Example 1 Synthesis of N-Phenylformamide with varying amounts of reaction solvent
1. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 100mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product of N-phenylformamide.
2. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 200mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
3. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
4. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 400mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
5. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 500mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
The product yield of N-phenylformamide obtained by the preparation methods described in the above 1 to 5 was calculated, and the results are shown in the following table 1:
table 1 process parameters of the preparation process and yield of the product N-phenylformamide as described in example 1
The mass spectrum of the main product obtained by the above reaction is shown in fig. 1 (the mass spectra of the main products of the above 5 reactions are the same, so only one mass spectrum is provided), and the structural formula is shown in the following formula 1. The above results show that N, N-dimethylformamide is used as a reaction solvent (the mass ratio of N, N-dimethylformamide to aniline is 100 to 500; meanwhile, when the mass ratio of the reaction solvent N, N-dimethylformamide to the aniline is 200-400.
Example 2 Synthesis of N-phenylformamide with varying reaction times
1. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 1 hour, and then filtering, distilling and recrystallizing to obtain the product N-phenylformamide.
2. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 2 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
3. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-phenylformamide.
4. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 12 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
5. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 36 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
The product yield of N-phenylformamide obtained by the preparation methods described in the above 1 to 5 was calculated, and the results are shown in the following table 2:
table 2 process parameters for the preparation and yield of the product N-phenylformamide as described in example 2
The mass spectrum of the main product obtained by the above reaction is shown in fig. 2 (the mass spectra of the main products of the above 5 reactions are the same, so only one mass spectrum is provided), and the structural formula is shown in the following formula 2. The result shows that under the condition that the reaction time is 1-36 hours, N-dimethylformamide is taken as a reaction solvent, oxygen is taken as an oxidant, zirconium hydroxide is taken as a catalyst, and aniline and the N, N-dimethylformamide can be catalyzed to carry out transamidation reaction to synthesize the N-phenylformamide; meanwhile, when the reaction time is 3-36 h, the yield of the N-phenylformamide obtained by the reaction is over 90 percent; and when the reaction time is 36h, the yield of the N-phenylformamide obtained by the reaction is up to 99%.
Example 3 Synthesis of N-phenylformamide with varying amounts of catalyst added
1. Adding 1.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
2. Adding 2.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-phenylformamide.
3. Adding 3.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
4. Adding 4.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
5. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
The product yield of N-phenylformamide obtained by the preparation methods described in the above 1 to 5 was calculated, and the results are shown in the following table 3:
table 3 process parameters for the preparation and yield of the product N-phenylformamide as described in example 3
The mass spectrum of the main product obtained by the above reaction is shown in fig. 3 (the mass spectra of the main products of the above 5 reactions are the same, so only one mass spectrum is provided), and the structural formula is shown in formula 3 below. The results show that N-phenyl formamide can be synthesized by performing a transamidation reaction on aniline and N, N-dimethylformamide as a reaction solvent, oxygen as an oxidant and zirconium hydroxide as a catalyst under the condition that the addition amount of the catalyst is 1.0-5.0 g; meanwhile, when the addition amount of the catalyst is 4.0-5.0 g, the yield of the N-phenylformamide obtained by the reaction is over 80 percent; and when the addition amount of the catalyst is 5.0g, the yield of the N-phenylformamide obtained by the reaction can reach 93%.
Example 4 Synthesis of N-phenylformamide at various reaction temperatures
1. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 100 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-phenylformamide.
2. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 110 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
3. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 130 ℃ to react for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-phenylformamide.
4. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 150 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
5. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
6. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 190 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
7. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 200 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-benzamide.
The product yields of N-phenylformamide obtained by the above-described preparation methods 1 to 7 were calculated, and the results are shown in table 4 below:
table 4 process parameters of the preparation process described in example 4 and yield of the product N-phenylcarboxamide
The mass spectrum of the main product obtained by the above reaction is shown in fig. 4 (the mass spectra of the main products of the above 7 reactions are the same, so only one mass spectrum is provided), and the structural formula is shown in formula 4 below. The results show that the N-phenyl formamide can be synthesized by performing transamidation reaction on aniline and N, N-dimethylformamide by taking N, N-dimethylformamide as a reaction solvent, oxygen as an oxidant and zirconium hydroxide as a catalyst at the reaction temperature of 100-200 ℃; meanwhile, when the reaction temperature is 150-200 ℃, the yield of the N-phenylformamide obtained by the reaction is over 70 percent; and when the reaction temperature is 170-200 ℃, the yield of the N-phenylformamide obtained by the reaction can reach over 90 percent.
Example 5 Synthesis of N-Phenylformamide in various atmospheres
1. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, plugging a rubber plug with a needle on the condenser tube to keep pressure balance, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product of N-phenylformamide.
2. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 9.3g of aniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-phenylformamide.
The product yield of N-phenylformamide obtained by the preparation methods described in 1 to 2 above was calculated, and the results are shown in table 5 below:
table 5 process parameters for the preparation and yield of the product N-phenylcarboxamide as described in example 5
The mass spectrum of the main product obtained by the above reaction is shown in fig. 5 (the mass spectra of the main products of the above 2 reactions are the same, so only one mass spectrum is provided), and the structural formula is shown in the following formula 5. The results show that N-phenyl formamide can be synthesized by performing transamidation reaction on aniline and N, N-dimethylformamide serving as a reaction solvent and zirconium hydroxide serving as a catalyst in the atmosphere of air, oxygen and nitrogen respectively; meanwhile, when the reaction atmosphere is oxygen, the yield of the N-phenylformamide obtained by the reaction can reach more than 90 percent;
EXAMPLE 6 Synthesis of N-phenylcarboxamides with different aniline derivatives
1. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 10.72g of o-toluidine and 300mL of N, N-dimethylformamide, inserting a condenser tube on the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N- (2-methylbenzene) formamide. The mass spectrum of the product is shown in FIG. 6, and the structural formula is shown in the following formula 6.
2. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 10.72g of m-methylaniline and 300mL of N, N-dimethylformamide, inserting a condenser tube on the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N- (3-methylbenzene) formamide. The mass spectrum of the product is shown in FIG. 7, and the structural formula is shown in the following formula 7.
3. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 10.72g of p-methylaniline and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N- (4-methylbenzene) formamide. The mass spectrum of the product is shown in figure 8, and the structural formula is shown in the following formula 8.
4. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 12.76g of parachloroaniline and 300mL of N, N-dimethylformamide, inserting a condenser tube on the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, exchanging air for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N- (4-chlorobenzene) formamide. The mass spectrum of the product is shown in figure 9, and the structural formula is shown in the following formula 9.
5. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 17.20g of p-bromoaniline and 300mL of N, N-dimethylformamide, inserting a condenser tube on the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, ventilating for 5-6 times to change the system into an oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N- (4-bromobenzene) formamide. The mass spectrum of the product is shown in figure 10, and the structural formula is shown in the following formula 10.
6. Adding 5.0g of zirconium hydroxide catalyst into a three-neck flask, adding 12.32g of p-anisidine and 300mL of N, N-dimethylformamide, inserting a condenser tube into the three-neck flask, inserting an oxygen-filled balloon on the condenser tube to ensure that the whole system is sealed and airtight, exchanging air for 5-6 times to change the system into oxygen atmosphere, heating and stirring at 170 ℃ for reaction for 3 hours, and then filtering, distilling and recrystallizing to obtain the product N-formyl-4-anisidine. The mass spectrum of the product is shown in FIG. 11, and the structural formula is shown in formula 11 below.
The product yields of the N-phenylcarboxamide derivatives obtained by the preparation methods described in the above 1 to 6 were calculated, and the results are shown in the following table 6:
table 6 process parameters and product yields for the preparation described in example 6
The mass spectrograms of the main products in the above reactions 1 to 6 are shown in FIGS. 6 to 11, respectively. The result shows that N, N-dimethylformamide is taken as a reaction solvent, oxygen is taken as an oxidant, zirconium hydroxide is taken as a catalyst, and the N- (2-methylbenzene) formamide can be synthesized by catalyzing o-toluidine with the yield of 39%; catalyzing m-methylaniline to synthesize N- (3-methylbenzene) formamide with the yield of 72 percent; catalyzing p-methylaniline to synthesize N- (4-methylbenzene) formamide, wherein the yield is 93%; catalyzing p-chloroaniline to synthesize N- (4-chlorobenzene) formamide with the yield of 47 percent; catalyzing p-bromoaniline to synthesize N- (4-bromobenzene) formamide with the yield of 36%; the N-formyl-4-methoxyaniline is synthesized by catalyzing p-methoxyaniline, and the yield is 94%. Therefore, the method can catalyze and synthesize the N-phenylformamide or the derivatives thereof by the aniline or the derivatives thereof, and the yield of the obtained target product is considerable.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. The application of zirconium hydroxide as a catalyst for catalyzing aniline or derivatives thereof to prepare N-phenylformamide or derivatives thereof.
2. The use according to claim 1, wherein the aniline or derivative thereof has the formula (i) and the N-phenylformamide or derivative thereof has the formula (ii):
wherein R is 1 ~R 5 Respectively selected from any one of hydrogen, halogen, hydroxyl, sulfonic group, nitro, substituted or unsubstituted straight chain or branched chain alkyl, alkoxy, carbonyl, alkenyl, alkynyl, substituted or unsubstituted aryl, acylamino and cyano.
3. The use of claim 2, wherein R is 1 ~R 5 Are respectively selected from hydrogen, methyl, chlorine, bromine and methoxyl.
4. A method for preparing N-phenylformamide or a derivative thereof, which is characterized by comprising the following steps: aniline or derivatives thereof shown in the following formula (I) is used as a raw material, N-Dimethylformamide (DMF) is used as a reaction solvent, zirconium hydroxide is used as a catalyst, oxygen is used as an oxidant, and the N-phenylformamide or derivatives thereof shown in the following formula (II) is synthesized through catalytic oxidation reaction;
wherein R is 1 ~R 5 Each selected from any one of hydrogen, halogen, hydroxyl, sulfonic acid group, nitro, substituted or unsubstituted straight chain or branched alkyl, alkoxy, carbonyl, alkenyl, alkynyl, substituted or unsubstituted aryl, acylamino and cyano.
5. The synthesis process according to claim 4, characterized in that the ratio of the catalyst to aniline or its derivatives is between 1 and 150g; the mass ratio of the reaction solvent to the aniline or the derivative thereof is 10-500; the reaction temperature is 100-200 ℃; the reaction time is 1-36 h.
6. The synthesis process according to claim 4, characterized in that the ratio of the catalyst used to aniline or its derivatives is 50g; the mass ratio of the reaction solvent to the aniline or the derivative thereof is 300; the reaction temperature is 170 ℃; the reaction time was 3h.
7. The method of claim 4, wherein R is 1 ~R 5 Are respectively selected from hydrogen, methyl, chlorine, bromine and methoxyl.
8. The method of claim 7, wherein the aniline or derivative thereof comprises: aniline, o-methylaniline, m-methylaniline, p-chloroaniline, p-bromoaniline and p-methoxyaniline.
9. The method of any one of claims 4 to 8, wherein the method comprises the steps of:
(1) Adding a zirconium hydroxide catalyst, aniline or a derivative thereof and N, N-dimethylformamide into a three-neck flask;
(2) Inserting a condenser tube on the three-mouth flask, inserting a balloon filled with oxygen into the mouth of the condenser tube, ensuring the whole system to be sealed, and reacting for 3 hours at 170 ℃;
(3) Filtering, distilling and recrystallizing to obtain the N-phenylformamide or the derivative thereof.
10. The process according to claim 9, wherein the catalyst is used in a ratio of 1 to 150g; the mass ratio of the reaction solvent to the aniline or the derivative thereof is 10-500; the oxygen is normal pressure, the reaction temperature is 100-200 ℃, and the reaction time is 1-36 h.
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