CN106000465B - A kind of method of aldehyde and the oxidative coupling reaction of two level amide - Google Patents

A kind of method of aldehyde and the oxidative coupling reaction of two level amide Download PDF

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CN106000465B
CN106000465B CN201610292240.2A CN201610292240A CN106000465B CN 106000465 B CN106000465 B CN 106000465B CN 201610292240 A CN201610292240 A CN 201610292240A CN 106000465 B CN106000465 B CN 106000465B
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aldehyde
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amide
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acetamide
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孙宏枚
吴钰锋
解存飞
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Suzhou University
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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    • B01J2531/842—Iron

Abstract

The invention discloses a kind of methods of aldehyde and the oxidative coupling reaction of two level amide.The present invention is efficiently catalyzed aldehyde with the oxidative coupling reaction of two level amide to prepare acid imide using the ionic iron of the Imidazole cation of functionalization containing single phenol (III) complex as catalyst for the first time, it not only can efficiently be catalyzed the oxidative coupling of aromatic aldehyde, aliphatic aldehyde and two level amide, it can also efficiently be catalyzed using aromatic heterocycle aldehyde and big steric hindrance two level amide as the oxidative coupling reaction of substrate, catalytic activity and substrate applicability are better than the prior art.

Description

A kind of method of aldehyde and the oxidative coupling reaction of two level amide
It is on July 27th, 2015 that the present invention, which is application No. is the 2015104452411, applying date, entitled " is contained Point of the patent application of ionic iron (III) complex of single phenol functionalization Imidazole cation and the preparation method and application thereof " Case application.
Technical field
The invention belongs to technical field of organic synthesis, specially a kind of ionic of the Imidazole cation of functionalization containing single phenol The method of the complex-catalyzed aldehyde of iron (III) and the oxidative coupling reaction of two level amide.
Background technology
The acid imide structural unit important as one is present in many natural products, and much effective knots of drug Structure unit, such as：Aniracetam, variotin etc..Therefore, how efficiently to build imide structure and receive more and more passes Note（Referring to：Y. J. Wang, C. Y. Chen, Z. Z. Huang,Chem. Eur. J., 2013, 19, 1129）. The coupling reaction of carboxylic acid derivates and amide is one of imido traditional mainstay of structure, but this method is often restricted In carboxylic acid derivates（Such as：Acyl chlorides）Unstability and poor Atom economy.（Referring to C. A. G. N. Montalbetti, V. Falque, Tetrahedron, 2005, 61, 10827）.As people are to the day of Green Chemistry Benefit is paid attention to, and finds the substitute of carboxylic acid derivates and becomes a hot spot in this research field.
Compared with carboxylic acid derivates, aldehyde compound has metastable chemical property, higher Atom economy The advantages that, this makes people start to be introduced into as the substitute of carboxylic acid derivates in imido structure.For example, with NBS (N- bromo-succinimides) is under conditions of oxidant, cuprous bromide can efficiently be catalyzed aromatic aldehyde and amide（Level-one Amide and two level amide）Oxidative coupling generate acid imide（Referring to L. Wang, H. Fu, Y. Y. Jiang, Y. F. Zhao, Chem. Eur. J., 2008, 14, 10772）；Using tert-butyl hydroperoxide as oxidant, two (triphenylphosphines) two Palladium can be catalyzed aromatic aldehyde and the two level amide of pyridine ring modification carries out oxidative coupling reaction, to prepare acid imide （Referring to Y. J. Wang, C. Y. Chen, Z. Z. Huang,Chem. Eur. J., 2013, 19, 1129）.These The result shows that replacing carboxylic acid derivates that there is good application prospect, still, existing method in imido synthesis with aldehyde There are some defects to have to be overcome, such as the expensive price of palladium series catalyst, the toxicity of Cu-series catalyst.Therefore, it develops inexpensive, low Malicious or nontoxic novel green catalyst is clearly very required.
Fe-series catalyst has many advantages, such as cheap, less toxic or nontoxic, preferable biocompatibility, develops Fe-series catalyst It is considered as developing the economy and a Critical policies of environment-friendly catalyst（Correa, A., Mancheño, O. G., Bolm, C., Chem. Soc. Rev.,2008, 37, 1108）.Using tert-butyl hydroperoxide as oxidant, dibrominated is ferrous The oxidative coupling that aromatic aldehyde, fatty aldehyde and two level amide can be catalyzed carrys out synthesizing imide（Referring to J. Wang, C. Liu, J. W. Yuan, A. W. Lei, Chem. Commun., 2014, 50, 4736）.This method can be catalyzed aldehyde and two level amide Oxidative coupling to prepare acid imide, but there are apparent drawback, mainly have：（1）Dibrominated ferrous iron is unstable, in air It is easy oxidation, deliquesces, it is inconvenient；（2）The purity of these molysite is often mixed with its of denier by its commercial source difference Its metal（Such as copper）, to cause the unstable of catalytic performance；（3）Substrate applicability need further to expand, such as due to virtue The reasons such as fragrant heterocyclic aldehydes hetero atom is coordinated with metal and the steric hindrance of big steric hindrance two level amide is larger, cause these substrates that can not have Effect carries out above-mentioned reaction.
For present inventor previous in research work, once design, which has synthesized, contains bisphenol functionalized imidazoles（Quinoline）Sun from Ionic iron (III) complex of son, it is found that they can be with effective catalyst aryl grignard reagent and containing the halogenated alkyl hydrocarbon of b-H Cross-coupling reaction（Referring to：(1)C. L. Xia, C. F. Xie, Y. F. Wu, H. M. Sun, Q. Shen, Y. Zhang, Org. Biomol. Chem., 2013, 11, 8135; (2)ZL201210397111.1）.Up to now, also not See the oxidation between ionic iron (III) complex and its catalysis aldehyde and two level amide of the Imidazole cation of functionalization containing single phenol The report of coupling reaction.
Invention content
The object of the present invention is to provide a kind of ionic iron (III) complex of Imidazole cation of functionalization containing single phenol, Its stable storage not only can efficiently be catalyzed the oxidative coupling of aromatic aldehyde, aliphatic aldehyde and two level amide to synthesize acyl Asia Amine, the oxidative coupling reaction that can be participated in efficient catalytic aromatic heterocycle aldehyde and big steric hindrance two level amide, catalytic activity and Substrate applicability is all significantly better than the prior art.
In order to achieve the above objectives, the technical solution adopted by the present invention is：The complex of formula I is catalyzed as single-component catalyst Aldehyde and two level amide carry out the application of oxidative coupling reaction；
Formula I；
Wherein R1For methyl or isopropyl；R2For hydrogen or methyl；R3For hydrogen or tertiary butyl；X is chlorine or bromine.
In above-mentioned technical proposal, catalyst amount is the 2%~5% of two level amide mole.Catalyst amount is less than existing Technology, but product yield high, purification are conveniently.
Ionic iron (III) complex for the Imidazole cation of functionalization containing single phenol that above-mentioned formula I indicates is as one-component The method of catalyst aldehyde and the oxidative coupling reaction of two level amide, includes the following steps：At room temperature, in inert gas atmosphere In, catalyst, two level amide, organic solvent, stirring is added into reactor successively；It then proceedes to sequentially add into reactor Aldehyde, tert-butyl hydroperoxide aqueous solution are stirred to react 18~36 hours in 60~80 DEG C to get to product.
In above-mentioned technical proposal, is terminated react with water after reaction；Reaction product is extracted with ethyl acetate, and passes through column layer Analysis（With ethyl acetate/petroleum ether volume ratio for 1:（5~20）Mixed solvent be solvent）Obtain product.
In above-mentioned technical proposal, the inert gas is nitrogen or argon gas；Organic solvent 1,2- dichloroethanes.
In above-mentioned technical proposal, the aldehyde is aromatic aldehyde, fatty aldehyde or aromatic heterocycle aldehyde, and the structure of aldehyde is RCHO, Middle aromatic aldehyde R is substituted-phenyl, and fatty aldehyde R is open chain aliphatic substitution, and aromatic heterocycle aldehyde R is heterocyclic substituent；Two level acyl Amine is chain amide, R4CONHR5, wherein R4For methyl or ethyl, R5For substituted-phenyl or alkyl substituent；And lactams.
In preferred technical solution, the aromatic aldehyde is the aldehyde compound with benzaldehyde skeleton structure, such as：Benzene first Aldehyde, o-tolualdehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, p-bromobenzaldehyde, 4-Fluorobenzaldehyde, p-tolyl aldehyde, 1- naphthalenes Formaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, terephthalaldehydic acid methyl esters Deng；The fatty aldehyde is the aldehyde compound with open chain alkane skeleton structure, such as：N-hexyl aldehyde, n-butanal etc.；The fragrance is miscellaneous Ring aldehyde is the aldehyde compound with aromatic heterocycle skeleton structure, such as：2 thiophene carboxaldehyde, 3- thiophenecarboxaldehydes or 2 furan carboxyaldehyde Deng；The chain amide is the substitution two level amide with open-chain structure, such as：NBenzylacetamide,NMethylacetamide,N- (2,4,6- trimethylphenyls) acetamide,N(2,6- diisopropyl phenyls) acetamide,N(2,6- diisopropyl phenyls) propionyl Amine,N(4- aminomethyl phenyls) acetamide,N(4- methoxyphenyls) acetamide,N(4- chlorphenyls) acetamide,N(4- fluoroforms Base phenyl) acetamide,NHexamethylene yl acetamide,NPhenylpropionamide etc.；The lactams is cyclic amide, such as：Caprolactam Deng.
In above-mentioned technical proposal, with molar amount, the dosage of aldehyde is 2.4 times of two level amide, tert-butyl hydroperoxide Dosage is 2 times of two level amide, and catalyst amount is 2%~5% mol of two level amide.Reaction time is 18 hours, reaction temperature Degree is 60 DEG C.
In preferred technical solution, with molar amount, aldehyde: two level amide: tert-butyl hydroperoxide: catalyst 2.4: 1: 2.0∶0.02；Reaction time is 18 hours, and reaction temperature is 60 DEG C.
It is described the invention also discloses a kind of ionic iron (III) complex of Imidazole cation of functionalization containing single phenol The chemical general formula of ionic iron (III) complex is [(Ar1NCH2CH2NAr2)CH][FeX4], wherein Ar1 = 2,6-di-R1- 4-R2-C6H2, Ar2 = 3,5-di-R3-2-(OH)-C6H2, R1One kind in methyl, isopropyl, R2Selected from hydrogen atom, first One kind in base, R3One kind in hydrogen atom, tertiary butyl, X are one kind in chlorine or bromine；Its structural formula is as shown in formula I：
Formula I.
In above-mentioned technical proposal, ionic iron (III) complex be the Imidazole cation of functionalization containing single phenol from Subtype iron (III) complex is prepared by single phenol functionalization imidazoline villaumite ligand with molysite.
The preparation method of ionic iron (III) complex of the above-mentioned Imidazole cation of functionalization containing single phenol, including it is following Step：Under the conditions of anhydrous and oxygen-free, in an inert gas atmosphere, molysite system is dissolved in single phenol functionalization imidazoline villaumite molten In agent, reacted 2~20 hours at 30~70 DEG C；Solvent is removed in vacuum, residue is extracted with tetrahydrofuran solvent, it is heavy to remove It forms sediment, iron (III) complex is recrystallized to give with the mixed solvent of hexane and tetrahydrofuran；The molysite system be ferric bromide with The mixture or ferric trichloride of sodium bromide.
When X is chlorine, the method for preparing above-mentioned ionic iron (III) complex includes the following steps：
It is in an inert gas atmosphere, ferric trichloride and single phenol functionalization imidazoline villaumite is molten under the conditions of anhydrous and oxygen-free In solvent, reacted 2~6 hours at 30~60 DEG C；Solvent is removed in vacuum, residue is extracted with tetrahydrofuran solvent, is removed Precipitation, iron (III) complex, the iron of as above-mentioned ionic are recrystallized to give with the mixed solvent of hexane and tetrahydrofuran (III) complex.
In above-mentioned technical proposal, the inert gas is nitrogen or argon gas, and the mixing of the hexane and tetrahydrofuran is molten The volume ratio of hexane and tetrahydrofuran is 1 in agent:4~1:15.
In preferred technical solution, the molar ratio of ferric trichloride and single phenol functionalization imidazoline villaumite is 1:1, solvent four Hydrogen furans, reaction temperature are 30 DEG C, and the reaction time is 4 hours.
When X is bromine, the method for preparing iron (III) complex of above-mentioned ionic includes the following steps：
Under the conditions of anhydrous and oxygen-free, in an inert gas atmosphere, by ferric bromide, single phenol functionalization imidazoline villaumite and bromine Change sodium to be dissolved in solvent, be reacted 10~20 hours at 45~70 DEG C；Solvent is removed in vacuum, is extracted with tetrahydrofuran solvent remaining Object removes precipitation, iron (III) complex, as above-mentioned ionic is recrystallized to give with the mixed solvent of tetrahydrofuran and hexane Iron (III) complex.
In above-mentioned technical proposal, the inert gas is nitrogen or argon gas, and the mixing of the hexane and tetrahydrofuran is molten The volume ratio of hexane and tetrahydrofuran is 1 in agent:4~1:15.
In preferred technical solution, the molar ratio of ferric bromide, single phenol functionalization imidazoline villaumite and sodium bromide is 1:1: 6, solvent is tetrahydrofuran, and reaction temperature is 45 DEG C, and the reaction time is 16 hours.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. ionic iron (III) complex of the Imidazole cation of functionalization containing single phenol disclosed by the invention can by The phenol oxygroup and alkyl for introducing different structure on two nitrogen-atoms of imidazoline ring respectively are realized to corresponding iron (III) complex The flexible modulation of steric hindrance and electronic effect, to develop a kind of new and effective Fe-series catalyst.
2. the present invention prepares work(containing single phenol by the reaction of molysite system and single phenol functionalization imidazoline villaumite under normal pressure Ionic iron (III) complex of Imidazole cation can be changed, reaction is simple to operation, and product is easily purified, yield is high, this kind of to match It is clear to close object structure, and can also be stabilized in air.
3. ionic iron (III) complex of the Imidazole cation of functionalization containing single phenol disclosed by the invention not only can be with Efficiently be catalyzed aromatic aldehyde, aliphatic aldehyde and two level amide oxidative coupling, can also efficiently be catalyzed with aromatic heterocycle aldehyde, Big steric hindrance two level amide is the oxidative coupling of substrate, and catalytic activity and substrate applicability are better than the prior art；The catalysis of the present invention Efficiency has a clear superiority compared with prior art, and the method for the present invention solves existing aromatic heterocycle aldehyde, big steric hindrance two level Amide can not effectively participate in the problem of reaction, and the method for the present invention need not add other ligands, and reaction system is simple, tool There is higher Atom economy；Be conducive to industrial applications.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Embodiment one：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 2- (OH)-C6H4, X=Cl）Synthesis
By 2,6- diisopropyl anilines（10.0 milliliters, 48 mMs）And triethylamine（7.3 milliliters, 48 mMs）It mixes molten In dried tetrahydrofuran, under ice-water bath, ethyl oxalyl chloride is slowly added dropwise（5.1 milliliters, 48 mMs）, it is added dropwise It stirs 5 hours at room temperature afterwards.Filtering, filtrate are washed three times with dilute hydrochloric acid, saturated salt solution respectively respectively, organic phase anhydrous slufuric acid Sodium is dried 12 hours.Organic phase is concentrated into saturation, and 100 milliliters of n-hexanes are added, there is solid precipitation, filters, dry, obtains white solid Body（N(diisopropyl phenyl) ethyl oxalate）, yield 92%.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 8.36 (s, 1H), 7.34 (t, 1H), 7.20 (d, 2H), 4.47-4.42 (m, 2H), 3.01 (m, 2H), 1.47 (t, 3H), 1.21 (d, 12H) ppm。
It willN(diisopropyl phenyl) ethyl oxalate（2.78 grams, 10.0 mMs）, Ortho-Aminophenol（1.31 grams, 12 millis Mole）And triethylamine（2.78 milliliters, 20 mMs）Mixing is dissolved in toluene, return stirring 12 hours.It is cooled to room temperature, reacts Liquid uses dilute hydrochloric acid, saturated common salt to wash three times respectively, and organic phase is dried 12 hours with anhydrous sodium sulfate.Organic phase is concentrated into full With, 100 milliliters of n-hexanes are added, there is solid precipitation, filter, it is dry, obtain white solid（N(2,6- diisopropyl phenyls)-N’- (2- hydroxy phenyls) oxamides）, yield 85%.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 9.67 (s, 1H), 8.84 (s, 1H), 8.12 (s, 1H), 7.50 (dd, 1H), 7.37 (t, 1H), 7.23 (d, 1H), 7.16 (dt, 1.5 Hz, 1H), 6.96-6.89 (m, 2H), 3.07-3.00 (m, 2H), 1.22 (d, 12H) ppm。
It takesN(2,6- diisopropyl phenyls)-N'-(2- hydroxy phenyl) oxamides（0.74 gram, 2.2 mMs）, thereto It is slowly added to borine tetrahydrofuran solution（17.6 milliliters, 1.0 mol/Ls, 17.6 mMs）Return stirring 12 hours.It is cooled to Room temperature is slowly added dropwise absolute methanol to no gas and generates, and concentrated hydrochloric acid is added（1.5 milliliters, 36%, 18 mM）, reaction solution rotation Do to obtain white solid.Ethyl orthoformate (10 milliliters) is added into white solid, is stirred 30 minutes at 90 DEG C, there is solid precipitation, Filtering, filter cake are washed three times with anhydrous ether, obtain white solid [(Ar1NCH2CH2NAr2)CH]Cl（Ar1=2,6-di-CH(CH3)2- C6H3, Ar2= 2-(OH)-C6H4）, yield 53%.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 9.04 (s, 1H), 7.57 (dd, 1H), 7.44 (t, 1H), 7.22 (d, 2H), 7.15 (d, 1H), 6.97 (dt, 1H), 6.78 (dt, 1H), 4.88 (t, 2H), 4.44 (t, 2H), 3.03-2.96 (m, 2H), 1.25 (d, 6H), 1.16 (d, 6H)ppm。
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 70.28 7.58 7.81
Actual value 70.03 7.42 7.73
Compound cation part [(Ar1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 323.2122, and theoretically 323.21, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is [(Ar1NCH2CH2NAr2)CH]Cl（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 2-(OH)-C6H4）.
By [(Ar1NCH2CH2NAr2)CH]Cl（0.36 gram, 1.0 mMs）It is added to ferric trichloride（0.16 gram, 1.0 millis Mole）Tetrahydrofuran solution in, reacted 4 hours at 30 DEG C, vacuum pumps solvent, and hexane washing is drained, extracted with tetrahydrofuran It takes, hexane recrystallization is added in clear liquid, yellowish-brown crystal, yield 92% are precipitated at room temperature for centrifugal clear liquid transfer.
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 48.40 5.22 5.38
Actual value 48.31 5.41 5.16
Since the complex of iron has paramagnetism, so not carrying out nuclear-magnetism characterization to it.
This complex [(Ar1NCH2CH2NAr2)CH][FeCl4] be in the form of ion pair existing for, wherein anion portion Divide [FeCl4]-It is characterized by Raman spectrum, in 333 cm-1There is characteristic peak at place.
The cationic portion [(Ar of complex1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 323.2141, and theoretically 323.21, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is target compound.
Embodiment two：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 2- (OH)-C6H4, X=Br）Synthesis
Successively by [(Ar1NCH2CH2NAr2)CH]Cl（0.36 gram, 1.0 mMs）And NaBr（0.62 gram, 6.0 mMs） It is added to ferric bromide（0.30 gram, 1.0 mMs）Tetrahydrofuran solution in, reacted 16 hours at 45 DEG C, vacuum pumps molten Agent, hexane washing, drains, is extracted with tetrahydrofuran, and hexane recrystallization is added in clear liquid, analyses at room temperature for centrifugal clear liquid transfer Go out red-brown crystals, yield 93%.
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 36.09 3.89 4.01
Actual value 36.32 4.15 3.92
This complex [(Ar1NCH2CH2NAr2)CH][FeBr4] be in the form of ion pair existing for, wherein anion portion Divide [FeBr4]-It is characterized by Raman spectrum, in 204 cm-1There is characteristic peak at place.
The cationic portion [(Ar of complex1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 323.2118, and theoretically 323.21, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is target compound.
Embodiment three：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5- di-C(CH3)3-2-(OH)-C6H2, X=Cl）Synthesis
[(Ar1NCH2CH2NAr2) CH] and Cl synthesis with reference to embodiment one the step of, utilize 3,5- di-t-butyl -2- hydroxyls Aniline replaces Ortho-Aminophenol.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 8.27 (s, 1H), 7.47 (t, 1H), 7.36 (d, 1H), 7.31 (s, 1H), 7.29 (s, 1H), 6.96 (d, 1H), 4.92 (t, 2H), 4.48 (t, 2H), 3.51- 3.40 (m, 2H), 1.44 (s, 9H), 1.37 (d, 6H), 1.30 (d, 15H)ppm。
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 73.93 9.20 5.95
Actual value 73.72 8.96 5.88
Compound cation part [(Ar1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 435.3384, and theoretically 435.34, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is [(Ar1NCH2CH2NAr2)CH]Cl（Ar1=2,6-di-CH(CH3)2-C6H3, Ar2= 3,5-di-C(CH3)3- 2-(OH)-C6H2）.
By [(Ar1NCH2CH2NAr2)CH]Cl（0.47 gram, 1.0 mMs）It is added to ferric trichloride（0.16 gram, 1.0 millis Mole）Tetrahydrofuran solution in, reacted 6 hours at 40 DEG C, vacuum pumps solvent, and hexane washing is drained, extracted with tetrahydrofuran It takes, hexane recrystallization is added in clear liquid, yellowish-brown crystal, yield 85% are precipitated at room temperature for centrifugal clear liquid transfer.
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 55.00 6.84 4.42
Actual value 55.36 6.53 4.63
This complex [(Ar1NCH2CH2NAr2)CH][FeCl4] be in the form of ion pair existing for, wherein anion portion Divide [FeCl4]-It is characterized by Raman spectrum, in 333 cm-1There is characteristic peak at place.
The cationic portion [(Ar of complex1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 435.3380, and theoretically 435.34, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is target compound.
Example IV：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5- di-C(CH3)3-2-(OH)-C6H2, X=Br）Synthesis
Successively by [(Ar1NCH2CH2NAr2)CH]Cl（0.47 gram, 1.0 mMs）And NaBr（0.62 gram, 6.0 mMs） It is added to ferric bromide（0.30 gram, 1.0 mMs）Tetrahydrofuran solution in, reacted 20 hours at 60 DEG C, vacuum pumps molten Agent, hexane washing, drains, is extracted with tetrahydrofuran, and hexane recrystallization is added in clear liquid, analyses at room temperature for centrifugal clear liquid transfer Go out red-brown crystals, yield 86%.
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 42.94 5.34 3.45
Actual value 43.27 5.46 3.56
This complex [(Ar1NCH2CH2NAr2)CH][FeBr4] be in the form of ion pair existing for, wherein anion portion Divide [FeBr4]-It is characterized by Raman spectrum, in 204 cm-1There is characteristic peak at place.
The cationic portion [(Ar of complex1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 435.3385, and theoretically 435.34, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is target compound.
Embodiment five：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1=2,4,6-tri-CH3-C6H2, Ar2=3,5-di-C (CH3)3-2-(OH)-C6H2, X=Cl）Synthesis
[(Ar1NCH2CH2NAr2) CH] and Cl synthesis with reference to embodiment one the step of, utilized for 2,4,6- trimethylaniline generations For 2,6- diisopropyl anilines；Ortho-Aminophenol is replaced using 3,5- di-t-butyl -2- hydroxyanilines.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 8.40 (s, 1H), 7.47 (t, 1H), 7.36 (d, 1H), 6.98 (s, 2H), 6.93 (d, 1H), 4.83 (t, 2H), 4.45 (t, 2H), 2.51 (s, 6H), 2.31 (s, 3H), 1.44 (s, 9H), 1.30 (s, 9H)ppm。
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 72.79 8.69 6.53
Actual value 72.71 8.55 6.61
Compound cation part [(Ar1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 393.2907, and theoretically 393.29, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is [(Ar1NCH2CH2NAr2)CH] Cl（Ar1 = 2,4,6-tri-CH3-C6H2, Ar2 = 3,5-di-C (CH3)3-2-(OH)-C6H2）.
By [(Ar1NCH2CH2NAr2)CH]Cl（0.43 gram, 1.0 mMs）It is added to ferric trichloride（0.16 gram, 1.0 millis Mole）Tetrahydrofuran solution in, reacted 2 hours at 60 DEG C, vacuum pumps solvent, and hexane washing is drained, extracted with tetrahydrofuran It takes, hexane recrystallization is added in clear liquid, yellowish-brown crystal, yield 82% are precipitated at room temperature for centrifugal clear liquid transfer.
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 52.82 6.31 4.74
Actual value 53.11 6.45 5.01
This complex [(Ar1NCH2CH2NAr2)CH][FeCl4] be in the form of ion pair existing for, wherein anion portion Divide [FeCl4]-It is characterized by Raman spectrum, in 333 cm-1There is characteristic peak at place.
The cationic portion [(Ar of complex1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 393.2906, and theoretically 393.29, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is target compound.
Embodiment six：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1=2,4,6-tri-CH3-C6H2, Ar2=3,5-di-C (CH3)3-2-(OH)-C6H2, X=Br）Synthesis
Successively by [(Ar1NCH2CH2NAr2)CH]Cl（0.43 gram, 1.0 mMs）And NaBr（0.62 gram, 6.0 mMs） It is added to ferric bromide（0.30 gram, 1.0 mMs）Tetrahydrofuran solution in, reacted 10 hours at 70 DEG C, vacuum pumps molten Agent, hexane washing, drains, is extracted with tetrahydrofuran, and hexane recrystallization is added in clear liquid, analyses at room temperature for centrifugal clear liquid transfer Go out red-brown crystals, yield 83%.
Elemental analysis is carried out to product, as a result as follows：
Elemental analysis
C：（%） H：（%） N：（%）
Theoretical value 40.61 4.85 3.64
Actual value 40.95 4.95 3.69
This complex [(Ar1NCH2CH2NAr2)CH][FeBr4] be in the form of ion pair existing for, wherein anion portion Divide [FeBr4]-It is characterized by Raman spectrum, in 204 cm-1There is characteristic peak at place.
The cationic portion [(Ar of complex1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its There are one molecular ion peaks at 393.2905, and theoretically 393.29, actual measurement substantially conforms to this molecular ion peak with theory.It proves Gained compound is target compound.
Embodiment seven：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1=2,6-di-CH(CH3)2-C6H3, Ar2=3,5-di-C (CH3)3-2-(OH)-C6H2, X=Br）The benzaldehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NBenzyl Yl acetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add benzaldehyde （122 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.It is anti-at 60 DEG C It answers 18 hours, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether body Product is solvent than the mixed solvent for being 1: 5）, yield 85%, catalytic efficiency 0.5974g/mmol/h.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.57-7.54 (m, 3H), 7.45-7.42 (m, 2H), 7.28- 7.24 (m, 5H), 5.00 (s, 2H), 2.16 (s, 3H) ppm。
Embodiment eight：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5- di-C(CH3)3-2-(OH)-C6H2, X=Br）The o-tolualdehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NBenzyl Yl acetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add o-methyl-benzene Formaldehyde（139 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.At 60 DEG C Reaction 18 hours is terminated with water and is reacted, and reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether The mixed solvent that volume ratio is 1: 10 is solvent）, yield 50%, catalytic efficiency 0.3708g/mmol/h.The substrate is existing Technology can not be prepared effectively, and this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.36-7.10 (m, 9H), 4.92 (s, 2H), 2.27 (s, 3H) , 2.19 (s, 3H) ppm。
Embodiment nine：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5- di-C(CH3)3-2-(OH)-C6H2, X=Br）The 4-chloro-benzaldehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（12.2 milligrams, 0.015 mM, 3mol%）,NBenzyl Yl acetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add to chlorobenzene first Aldehyde（168.7 milligrams, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.At 60 DEG C Reaction 18 hours is terminated with water and is reacted, and reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether The mixed solvent that volume ratio is 1: 10 is solvent）, yield 93%, catalytic efficiency 0.4943g/mmol/h.The substrate is existing Technology is purified through column chromatography, yield 61%, catalytic efficiency 0.2188g/mmol/h, and this method has compared with the prior art Clear superiority.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.49 (d, 2H), 7.39 (d, 2H), 7.33-7.14 (m, 5H), 4.98 (s, 2H), 2.19 (s, 3H) ppm。
Embodiment ten：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5- di-C(CH3)3-2-(OH)-C6H2, X=Br）The p-bromobenzaldehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（20.3 milligrams, 0.025 mM, 5 mol%）,N- Benzylacetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add to bromobenzene Formaldehyde（220.0 milligrams, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.60 It is reacted 18 hours at DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/stone The mixed solvent that oily ether volume ratio is 1: 20 is solvent）, yield 82%, catalytic efficiency 0.3225g/mmol/h.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.55 (d, 2H), 7.41 (d, 2H), 7.31 -7.17 (m, 5H), 4.98 (s, 2H), 2.19 (s, 3H) ppm。
Embodiment 11：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The o-chlorobenzaldehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（20.3 milligrams, 0.025 mM, 5mol%）,NBenzyl Yl acetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add adjacent chlorobenzene first Aldehyde（135 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.It is anti-at 80 DEG C It answers 36 hours, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether body Product is solvent than the mixed solvent for being 1: 10）, yield 73%, catalytic efficiency 0.4029g/mmol/h.The existing skill of the substrate Art is purified through column chromatography, yield 43%, catalytic efficiency 0.3587g/mmol/h, and this method has bright compared with the prior art Aobvious advantage.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.41-7.31 (m, 2H), 7.27-7.21 (m, 4H), 7.11- 7.07 (m, 3H), 4.90 (s, 2H), 2.41 (s, 3H) ppm。
Embodiment 12：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The 4-Fluorobenzaldehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（20.3 milligrams, 0.025 mM, 5 mol%）,N- Benzylacetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add to fluorobenzene Formaldehyde（129 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.At 60 DEG C Lower reaction 36 hours, is terminated with water and is reacted, and reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/oil The mixed solvent that ether volume ratio is 1: 20 is solvent）, yield 86%, catalytic efficiency 0.1295g/mmol/h.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.60-7.56 (m, 2H), 7.30-7.20 (m, 5H), 7.10 (d, 2H), 4.99 (s, 2H), 2.18 (s, 3H) ppm。
Embodiment 13：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The 1- naphthaldehydes of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（20.3 milligrams, 0.025 mM, 5 mol%）,N- Benzylacetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add 1- naphthalene first Aldehyde（162 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.It is reacted at 70 DEG C It 36 hours, is terminated and is reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether volume Than being solvent for 1: 10 mixed solvent）, yield 53%, catalytic efficiency 0.1784g/mmol/h.The substrate prior art It can not effectively prepare, this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.96-7.92 (m, 2H), 7.88-7.85 (m, 1H), 7.54- 7.53 (m, 2H), 7.41-7.33 (m, 2H), 7.26-6.95 (m, 5H), 4.97 (s, 2H), 2.23 (s, 3H) ppm。
Embodiment 14：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The terephthalaldehydic acid methyl esters of catalysis andNThe oxidative coupling of benzylacetamide Reaction
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NBenzyl Yl acetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add to aldehyde radical benzene Methyl formate（197.1 milligrams, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）. It is reacted 18 hours at 60 DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With acetic acid second The mixed solvent that ester/petroleum ether volume ratio is 1: 10 is solvent）, yield 83%, catalytic efficiency 0.7170g/mmol/h. The substrate prior art can not be prepared effectively, and this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 8.07 (d, 2H), 7.56 (d, 2H), 7.28-7.17 (m, 5H), 4.98 (s, 2H), 3.92 (s, 3H), 2.22 (s, 3H) ppm。
Embodiment 15：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The 2 thiophene carboxaldehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（20.3 milligrams, 0.025 mM, 5 mol%）,N- Benzylacetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add 2- thiophene Formaldehyde（111 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.At 80 DEG C Lower reaction 30 hours, is terminated with water and is reacted, and reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/oil The mixed solvent that ether volume ratio is 1: 5 is solvent）, yield 47%, catalytic efficiency 0.1122g/mmol/h.The substrate is existing There is technology not prepare effectively, this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.56-7.55 (m, 1H), 7.38-7.37 (d, 1H), 7.24- 7.16 (m, 5H), 6.99-6.97 (m, 1H), 4.99 (s, 2H), 2.18 (s, 3H)。
Embodiment 16：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The 3- thiophenecarboxaldehydes of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NBenzyl Yl acetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add 3- thiophene first Aldehyde（106 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.At 60 DEG C Reaction 18 hours is terminated with water and is reacted, and reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether The mixed solvent that volume ratio is 1: 10 is solvent）, yield 67%, catalytic efficiency is 0.1928 g/mmol/h.The substrate is existing There is technology not prepare effectively, this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.74-7.73 (d, 1H), 7.32-7.21 (m, 7H), 5.01 (s, 2H), 2.23 (s, 3H) ppm。
Embodiment 17：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The 2 furan carboxyaldehyde of catalysis andNThe oxidative coupling reaction of benzylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NBenzyl Yl acetamide（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add 2- furans first Aldehyde（99 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.It is reacted at 60 DEG C It 36 hours, is terminated and is reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether volume Than being solvent for 1: 10 mixed solvent）, yield 43%, catalytic efficiency is 0.2903 g/mmol/h.The existing skill of the substrate Art can not be prepared effectively, and this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.71-7.70 (m, 1H), 7.58-7.57 (m, 1H), 7.43- 7.41 (d, 1H), 7.31-7.23 (m, 2H), 7.17-7.16 (m, 1H), 6.92-6.91 (m, 1H), 6.55- 6.54 (m, 1H), 5.08 (s, 2H), 2.24 (s, 3H) ppm。
Embodiment 18：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The n-hexyl aldehyde of catalysis andNThe oxidative coupling reaction of benzyl phenyl-acetamides
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NBenzyl Phenyl-acetamides（74.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add n-hexyl aldehyde （147 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.It is anti-at 60 DEG C It answers 18 hours, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether body Product is solvent than the mixed solvent for being 1: 20）, yield 71%, catalytic efficiency 0.6861g/mmol/h.The existing skill of the substrate Art is purified through column chromatography, yield 47%, and catalytic efficiency is 0.1451g/mmol/h this method to be had obviously compared with the prior art Advantage.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.37-7.28 (m, 3H), 7.16 (d, 2H), 4.99 (s, 2H),2.69 (t, 2H), 2.46 (s, 3H), 1.67-1.63 (m, 2H), 1.31-1.28 (m, 4H), 0.89 (t, 3H) ppm。
Embodiment 19：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The benzaldehyde of catalysis andNThe oxidative coupling reaction of phenyl-acetamides
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NBenzene Yl acetamide（67.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add benzaldehyde （122 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.It is reacted at 60 DEG C It 18 hours, is terminated and is reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether volume Than being solvent for 1: 5 mixed solvent）, yield 80%, catalytic efficiency 0.5112g/mmol/h.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.64 (d, 2H), 7.43-7.20 (m, 6H), 7.18 (d, 2H) 2.46 (s, 3H) ppm。
Embodiment 20：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3, 5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The benzaldehyde of catalysis andNThe oxidative coupling reaction of methylacetamide
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,NFirst Yl acetamide（36.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add benzaldehyde （122 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.It is anti-at 60 DEG C It answers 18 hours, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether body Product is solvent than the mixed solvent for being 1: 10）, yield 85%, catalytic efficiency 0.4132g/mmol/h.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.64–7.47 (m, 5H), 3.22 (s, 3H), 2.34 (s, 3H) ppm。
Embodiment 21：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The benzaldehyde of catalysis andNThe oxygen of (2,4,6- trimethylphenyls) acetamide Change coupling reaction
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,N- (2,4,6- trimethylphenyls) acetamide（88.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stirring 2 minutes, then Sequentially add benzaldehyde（122 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mmoles You）.It is reacted 18 hours at 60 DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With acetic acid The mixed solvent that ethyl ester/petroleum ether volume ratio is 1: 10 is solvent）, yield 97%, catalytic efficiency 0.7571g/mmol/ h。
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.61-7.59 (m, 2H), 7.42-7.38 (t, 1H), 7.33- 7.30 (d, 3H), 6.89 (s, 2H), 2.24 (s, 3H), 2.20-2.19 (d, 9H) ppm。
Embodiment 22：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The benzaldehyde of catalysis andNThe oxygen of (2,6- diisopropyl phenyls) acetamide Change coupling reaction
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,N- (2,6- diisopropyl phenyls) acetamide（109.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stirring 2 minutes, Sequentially add benzaldehyde（122 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 millis Mole）.It is reacted 18 hours at 60 DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With second The mixed solvent that acetoacetic ester/petroleum ether volume ratio is 1: 10 is solvent）, yield 97%, catalytic efficiency 0.8703g/ mmol/h.The substrate prior art can not be prepared effectively, and this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.64-7.62 (m, 2H), 7.46-7.35 (m, 4H), 7.24- 7.22 (d, 2H), 3.12-3.02 (m, 2H), 2.13 (s, 3H), 1.25-1.23 (d, 6H) , 1.16-1.14 (d, 6H) ppm。
Embodiment 23：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The benzaldehyde of catalysis andNThe oxygen of (2,6- diisopropyl phenyls) propionamide Change coupling reaction
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）,N- (2,6- diisopropyl phenyls) propionamide（117.4 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stirring 2 minutes, Sequentially add benzaldehyde（122 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mmoles You）.It is reacted 18 hours at 60 DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With acetic acid The mixed solvent that ethyl ester/petroleum ether volume ratio is 1: 10 is solvent）, yield 62%, catalytic efficiency 0.5804g/mmol/ h.The substrate prior art can not be prepared effectively, and this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.63-7.61 (d, 2H), 7.46-7.37 (m, 4H), 7.25- 7.23 (d, 2H), 3.12-3.02 (m, 2H), 2.36-2.31 (m, 2H), 1.24-1.22 (d, 6H) , 1.16- 1.14 (d, 6H) , 1.09-1.05 (t, 3H)ppm。
Embodiment 24：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The benzaldehyde of catalysis and the oxidative coupling reaction of caprolactam
In reaction bulb, catalyst is sequentially added under argon gas protection（8.1 milligrams, 0.010 mM, 2 mol%）, in oneself Amide（56.6 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stir 2 minutes, sequentially add benzaldehyde（122 is micro- It rises, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mMs）.Reaction 24 is small at 70 DEG C When, it is terminated and is reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With ethyl acetate/petroleum ether volume ratio for 1: 10 mixed solvent is solvent）, yield 96%, catalytic efficiency 0.4341g/mmol/h.The substrate prior art is through column layer Analysis separation, yield 67%, catalytic efficiency 0.1817g/mmol/h, this method have a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.56-7.53 (m, 2H), 7.46-7.37 (m, 3H), 4.00- 3.97 (m, 2H), 2.71-2.68 (m, 2H), 1.85-1.83 (m, 6H)ppm。
Embodiment 25：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The p-tolyl aldehyde of catalysis andN(2,6- diisopropyl phenyls) acetyl The oxidative coupling reaction of amine
In reaction bulb, catalyst is sequentially added under argon gas protection（16.2 milligrams, 0.020 mM, 4 mol%）,N- (2,6- diisopropyl phenyls) acetamide（109.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stirring 2 minutes, Sequentially add p-tolyl aldehyde（142 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mM）.It is reacted 24 hours at 70 DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, and column chromatography carries It is pure（Using ethyl acetate/petroleum ether volume ratio be 1: 5 mixed solvent as solvent）, yield 89%, catalytic efficiency is 0.2995g/mmol/h。
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.65-7.63 (d, 2H), 7.49-7.45 (t, 1H), 7.32- 7.26 (m, 4H), 3.20-2.10 (m, 2H), 2.45 (s, 3H), 2.22 (s, 3H),1.33-1.31 (d, 6H) , 1.23-1.22 (d, 6H) ppm。
Embodiment 26：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The 1- naphthaldehydes of catalysis andN(2,6- diisopropyl phenyls) acetamide Oxidative coupling reaction
In reaction bulb, catalyst is sequentially added under argon gas protection（12.2 milligrams, 0.015 mM, 3 mol%）,N- (2,6- diisopropyl phenyls) acetamide（109.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stirring 2 minutes, Sequentially add 1- naphthaldehydes（162 microlitres, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 millis Mole）.It is reacted 28 hours at 80 DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, column chromatography purification（With second The mixed solvent that acetoacetic ester/petroleum ether volume ratio is 1: 10 is solvent）, yield 81%, catalytic efficiency 0.4441g/ mmol/h.The substrate prior art can not be prepared effectively, and this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 8.05-8.03 (d, 1H), 7.90-7.85 (q, 1H), 7.58- 7.41 (m, 5H), 7.31 (s, 1H), 7.29 (s, 1H),3.25-3.15 (m, 2H), 1.96 (s, 3H), 1.30-1.27 (t, 12H) ppm。
Embodiment 27：[(Ar1NCH2CH2NAr2)CH][FeX4]（Ar1 = 2,6-di-CH(CH3)2-C6H3, Ar2 = 3,5-di-C(CH3)3-2-(OH)-C6H2, X=Br）The p-bromobenzaldehyde of catalysis andN(2,6- diisopropyl phenyls) acetamide Oxidative coupling reaction
In reaction bulb, catalyst is sequentially added under argon gas protection（16.2 milligrams, 0.020 mM, 4 mol%）,N- (2,6- diisopropyl phenyls) acetamide（109.5 milligrams, 0.5 mM）, 2.0 milliliters of 1,2- dichloroethanes, stirring 2 minutes, Sequentially add p-bromobenzaldehyde（220.0 milligrams, 1.2 mMs）, 70% tert-butyl hydroperoxide aqueous solution（136 microlitres, 1.0 mM）.It is reacted 18 hours at 60 DEG C, is terminated and reacted with water, reaction product is extracted with ethyl acetate, and column chromatography carries It is pure（Using ethyl acetate/petroleum ether volume ratio be 1: 10 mixed solvent as solvent）, yield 93%, catalytic efficiency is 0.5193g/mmol/h.The substrate prior art can not be prepared effectively, and this method has a clear superiority compared with the prior art.
Product is dissolved in CDCl3In（About 0.4 mL）, tube sealing measures on Unity Inova-400 type NMR instrument at room temperature Characterization：1H NMR (400 MHz, CDCl3, TMS): 7.55-7.48 (q, 4H), 7.43-7.39 (t, 1H), 7.26- 7.24 (t, 2H), 3.07-2.98 (m, 2H), 2.11 (s, 3H), 1.25-1.24 (d, 6H) , 1.15-1.13 (d, 6H) ppm。

Claims (5)

1. ionic iron (III) complex of the Imidazole cation of functionalization containing single phenol is catalyzed aldehyde and two as single-component catalyst The method of the oxidative coupling reaction of grade amide, includes the following steps：At room temperature, in an inert gas atmosphere, successively to reactor Middle addition catalyst, two level amide, organic solvent, stirring；It then proceedes to sequentially add aldehyde, tert-butyl hydroperoxide into reactor Aqueous solution of hydrogen is stirred to react 18~36 hours in 60~80 DEG C；It is terminated and is reacted with water after reaction；Reaction product acetic acid second Ester extracts, and product is obtained by column chromatography；Ionic iron (III) complex of the Imidazole cation of functionalization containing single phenol Structural formula with formula I：
Formula I；
Wherein R1For methyl or isopropyl；R2For hydrogen or methyl；R3For hydrogen or tertiary butyl；X is chlorine or bromine；
The aldehyde is aromatic aldehyde, fatty aldehyde or aromatic heterocycle aldehyde；Two level amide is chain amide or lactams.
2. according to the method described in claim 1, it is characterized in that：The inert gas is nitrogen or argon gas；It is described organic Solvent is 1,2- dichloroethanes.
3. according to the method described in claim 1, it is characterized in that：With molar amount, aldehyde: two level amide: tert-butyl hydroperoxide Hydrogen: catalyst 2.4: 1: 2.0:（0.02~0.05）；Reaction time is 18 hours, and reaction temperature is 60 DEG C.
4. according to the method described in claim 1, it is characterized in that：With molar amount, aldehyde: two level amide: tert-butyl hydroperoxide Hydrogen: catalyst 2.4: 1: 2.0: 0.02.
5. according to the method described in claim 1, it is characterized in that：The aldehyde is benzaldehyde, o-tolualdehyde, to chlorobenzene first Aldehyde, p-bromobenzaldehyde, o-chlorobenzaldehyde, 4-Fluorobenzaldehyde, terephthalaldehydic acid methyl esters, 1- naphthaldehydes, 2 thiophene carboxaldehyde, 3- thiophenes Pheno formaldehyde, 2 furan carboxyaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, just oneself Aldehyde or n-butanal；The two level amide isNBenzylacetamide,NMethylacetamide,N(2,4,6- trimethylphenyls) acetyl Amine,N(2,6- diisopropyl phenyls) acetamide,N(2,6- diisopropyl phenyls) propionamide,N(4- aminomethyl phenyls) acetyl Amine,N(4- methoxyphenyls) acetamide,N(4- chlorphenyls) acetamide,N(4- trifluoromethyls) acetamide,NHexamethylene Yl acetamide,NPhenylpropionamide or caprolactam.
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