CN106000465A - Method for oxidative coupling reaction of aldehyde and secondary amide - Google Patents

Method for oxidative coupling reaction of aldehyde and secondary amide Download PDF

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CN106000465A
CN106000465A CN201610292240.2A CN201610292240A CN106000465A CN 106000465 A CN106000465 A CN 106000465A CN 201610292240 A CN201610292240 A CN 201610292240A CN 106000465 A CN106000465 A CN 106000465A
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aldehyde
amide
reaction
acetamide
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孙宏枚
吴钰锋
解存飞
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Suzhou University
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Abstract

The invention discloses a method for an oxidative coupling reaction of aldehyde and secondary amide. An ionic iron (III) complex containing a monophenol functional imidazole cation serves as a catalyst to efficiently catalyze the oxidative coupling reaction of aldehyde and secondary amide to prepare imide for the first time; not only can oxidative coupling of aromatic aldehyde, aliphatic aldehyde and secondary amide be efficiently catalyzed, but also an oxidative coupling reaction taking aromatic heterocyclic aldehyde and large steric hindrance secondary amide as substrates can be efficiently catalyzed, and the catalytic activity and substrate applicability are superior to those in the prior art.

Description

A kind of method of the oxidative coupling reaction of aldehyde and two grades of amide
The present invention is Application No. 2015104452411, filing date on July 27th, 2015, invention entitled " contains Ionic iron (III) coordination compound of single phenol functionalization Imidazole cation and preparation method and application " patent application point Case application.
Technical field
The invention belongs to technical field of organic synthesis, a kind of ion-type containing single phenol functionalization Imidazole cation Aldehyde that ferrum (III) is complex-catalyzed and the method for the oxidative coupling reaction of two grades of amide.
Background technology
Acid imide is present in many natural products as an important construction unit, is also effective knot of a lot of medicine Structure unit, such as: aniracetam, variotin etc..Therefore, build imide structure the most efficiently and receive increasing pass Note (see: 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 to build one of imido traditional mainstay, but this method is the most restricted Unstability and poor Atom economy in carboxylic acid derivates (such as: acyl chlorides).(see C. A. G. N. Montalbetti, V. Falque, Tetrahedron, 2005,61,10827).Along with people's day to Green Chemistry Benefit is paid attention to, and the substitute finding carboxylic acid derivates becomes a focus in this research field.
Compared with carboxylic acid derivates, aldehyde compound has metastable chemical property, higher Atom economy Etc. advantage, this makes people start as the succedaneum of carboxylic acid derivates to be incorporated in imido structure.Such as, with Under conditions of NBS (N-bromo-succinimide) is oxidant, cuprous bromide can be catalyzed aromatic aldehyde and amide (one-level efficiently Amide and two grades of amide) oxidative coupling generate acid imide and (see L. Wang, H. Fu, Y. Y. Jiang, Y. F. Zhao, Chem. Eur. J., 2008,14,10772)；With tert-butyl hydroperoxide as oxidant, two (triphenylphosphines) two Palladium can be catalyzed two grades of amide of aromatic aldehyde and pyridine ring modification and carry out oxidative coupling reaction, thus prepares acid imide (see Y. J. Wang, C. Y. Chen, Z. Z. Huang,Chem. Eur. J., 2013,19,1129).These Result shows to replace carboxylic acid derivates to have good application prospect in imido synthesis with aldehyde, but, existing method is also Some defects are had to have to be overcome, such as expensive price, the toxicity etc. of Cu-series catalyst of palladium series catalyst.Therefore, develop inexpensive, low Malicious or nontoxic novel green catalyst is clearly the most required.
The advantages such as Fe-series catalyst has inexpensively, low toxicity or nontoxic, preferable biocompatibility, develop Fe-series catalyst Be considered as develop the economy and environment-friendly catalyst a Critical policies (Correa, A., Manche o, O. G., Bolm, C., Chem. Soc. Rev.,2008,37,1108).With tert-butyl hydroperoxide as oxidant, dibrominated is ferrous The oxidative coupling of aromatic aldehyde, fatty aldehyde and two grades of amide can be catalyzed carry out synthesizing imide and (see J. Wang, C. Liu, J. W. Yuan, A. W. Lei, Chem. Commun., 2014,50,4736).The method can be catalyzed aldehyde and two grades of amide Oxidative coupling to prepare acid imide, but there is obvious drawback, mainly have: (1) dibrominated ferrous iron is unstable, in atmosphere Easily oxidation, deliquescence, operation inconvenience；(2) purity of these iron salt is often mixed with its of denier by its commercial source difference Its metal (such as copper) thus cause the instability of catalytic performance；(3) substrate applicability need to expand further, as due to virtue Fragrant heterocyclic aldehydes hetero atom is the reason such as bigger with the steric hindrance of metal-complexing and big two grades of amide of steric hindrance, causes these substrates to have Effect carries out above-mentioned reaction.
In present inventor's research work previously, once design synthesized containing bisphenol functionalized imidazoles (quinoline) sun from Ionic iron (III) coordination compound of son, finds that they can be with effective catalyst aryl grignard reagent and the halogenated alkyl hydrocarbon containing b-H Cross-coupling reaction (see: (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, the most not See the oxidation between ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation and catalysis aldehyde and two grades of amide The report of coupling reaction.
Summary of the invention
It is an object of the invention to provide a kind of ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation, Its stable storage, is possible not only to the oxidative coupling being catalyzed aromatic aldehyde, aliphatic aldehyde and two grades of amide efficiently sub-to synthesize acyl Amine, it is also possible to the oxidative coupling reaction that efficient catalytic aromatic heterocycle aldehyde and two grades of amide of big steric hindrance participate in, its catalysis activity and Substrate applicability is all significantly better than prior art.
For reaching above-mentioned purpose, the technical solution used in the present invention is: the coordination compound of formula I is catalyzed as single-component catalyst Aldehyde and two grades of amide carry out the application of oxidative coupling reaction；
Formula I；
Wherein R1For methyl or isopropyl；R2For hydrogen or methyl；R3For hydrogen or the tert-butyl group；X is chlorine or bromine.
In technique scheme, catalyst amount is the 2%～5% of two grades of amide moles.Catalyst amount is less than existing Technology, but product yield is high, it is convenient to purify.
Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation that above-mentioned formula I represents is as one-component The method of the oxidative coupling reaction of catalyst aldehyde and two grades of amide, comprises the following steps: under room temperature, at inert gas atmosphere In, in reactor, add catalyst, two grades of amide, organic solvents, stirring successively；Then proceed to be sequentially added in reactor Aldehyde, tert-butyl hydroperoxide aqueous solution, in 60～80 DEG C of stirring reactions 18～36 hours, i.e. obtain product.
In technique scheme, reaction terminates reaction with water after terminating；Product is extracted with ethyl acetate, by post layer Analysis (with ethyl acetate/petroleum ether volume ratio for 1: the mixed solvent of (5～20) is as developing solvent) i.e. obtains product.
In technique scheme, described noble gas is nitrogen or argon；Organic solvent 1,2-dichloroethanes.
In technique scheme, described aldehyde is aromatic aldehyde, fatty aldehyde or aromatic heterocycle aldehyde, and the structure of aldehyde is RCHO, its 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 grades of acyls Amine is chain amide, R4CONHR5, wherein R4For methyl or ethyl, R5For substituted-phenyl or alkyl substituent；And lactams.
Preferably in technical scheme, described aromatic aldehyde is the aldehyde compound with benzaldehyde framing structure, such as: benzene first Aldehyde, o-tolualdehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, p-bromobenzaldehyde, 4-Fluorobenzaldehyde, p-tolyl aldehyde, 1-naphthalene Formaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, terephthalaldehydic acid methyl ester Deng；Described fatty aldehyde is the aldehyde compound with open chain alkane framing structure, such as: n-hexyl aldehyde, hutanal etc.；Described fragrance is miscellaneous Ring aldehyde is the aldehyde compound with aromatic heterocycle framing structure, such as: 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde or 2 furan carboxyaldehyde Deng；Described chain amide is two grades of amide of replacement with open-chain structure, such as:N-benzylacetamide,N-methylacetamide,N-(2,4,6-trimethylphenyl) acetamide,N-(2,6-diisopropyl phenyl) acetamide,N-(2,6-bis-is different Propyl group phenyl) propionic acid amide.,N-(4-aminomethyl phenyl) acetamide,N-(4-methoxyphenyl) acetamide,N-(4-chlorphenyl) Acetamide,N-(4-trifluoromethyl) acetamide,N-cyclohexyl acetamide,N-Phenylpropionamide etc.；Described lactams is Cyclic amide, such as: caprolactam etc..
In technique scheme, with molar amount, the consumption of aldehyde is 2.4 times of two grades of amide, tert-butyl hydroperoxide Consumption is 2 times of two grades of amide, and catalyst amount is 2%～5% mol of two grades of amide.Response time is 18 hours, reaction temperature Degree is 60 DEG C.
Preferably in technical scheme, with molar amount, aldehyde: two grades of amide: tert-butyl hydroperoxide: catalyst is 2.4: 1: 2.0∶0.02；Response time is 18 hours, and reaction temperature is 60 DEG C.
The invention also discloses a kind of ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation, described The chemical general formula of ionic iron (III) coordination compound is [(Ar1NCH2CH2NAr2)CH][FeX4], wherein Ar1 = 2,6-di-R1- 4-R2-C6H2, Ar2 = 3,5-di-R3-2-(OH)-C6H2, R1One in methyl, isopropyl, R2Selected from hydrogen atom, first One in base, R3One in hydrogen atom, the tert-butyl group, X is the one in chlorine or bromine；Its structural formula is as shown in formula I:
Formula I.
In technique scheme, described ionic iron (III) coordination compound be containing single phenol functionalization Imidazole cation from Subtype ferrum (III) coordination compound, it is prepared with iron salt by single phenol functionalization imidazoline villaumite part.
The preparation method of above-mentioned ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation, including following Step: under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, is dissolved in molten by iron salt system with single phenol functionalization imidazoline villaumite In agent, react 2～20 hours at 30～70 DEG C；Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, and it is heavy to remove Form sediment, be recrystallized to give ferrum (III) coordination compound with the mixed solvent of hexane and oxolane；Described iron salt system be ferric bromide with The mixture of sodium bromide or ferric chloride.
When X is chlorine when, the method preparing above-mentioned ionic iron (III) coordination compound comprises the following steps:
Under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, ferric chloride is dissolved in molten with single phenol functionalization imidazoline villaumite In agent, react 2～6 hours at 30～60 DEG C；Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, removes precipitation, Being recrystallized to give ferrum (III) coordination compound with the mixed solvent of hexane and oxolane, the ferrum (III) being above-mentioned ion-type coordinates Thing.
In technique scheme, described noble gas is nitrogen or argon, and the mixing of described hexane and oxolane is molten In agent, the volume ratio of hexane and oxolane is 1:4～1:15.
Preferably in technical scheme, ferric chloride is 1:1 with the mol ratio of single phenol functionalization imidazoline villaumite, and solvent is four Hydrogen furan, reaction temperature is 30 DEG C, and the response time is 4 hours.
When X is bromine when, the method for ferrum (III) coordination compound preparing above-mentioned ion-type comprises the following steps:
Under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, by ferric bromide, single phenol functionalization imidazoline villaumite and sodium bromide It is dissolved in solvent, reacts 10～20 hours at 45～70 DEG C；Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, Remove precipitation, be recrystallized to give ferrum (III) coordination compound with the mixed solvent of oxolane and hexane, be above-mentioned ionic iron (III) coordination compound.
In technique scheme, described noble gas is nitrogen or argon, and the mixing of described hexane and oxolane is molten In agent, the volume ratio of hexane and oxolane is 1:4～1:15.
Preferably in technical scheme, the mol ratio of ferric bromide, single phenol functionalization imidazoline villaumite and sodium bromide is 1:1: 6, solvent is oxolane, and reaction temperature is 45 DEG C, and the response time is 16 hours.
Owing to technique scheme is used, the present invention compared with prior art has the advantage that
Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation the most disclosed by the invention can be by imidazoles The phenol epoxide and the alkyl that introduce different structure on two nitrogen-atoms of quinoline ring respectively realize the space to corresponding ferrum (III) coordination compound Steric hindrance and the flexible modulation of electronic effect, thus develop the Fe-series catalyst that a class is new and effective.
2. the present invention contains single phenol merit by iron salt system and the reaction preparation at ambient pressure of single phenol functionalization imidazoline villaumite Can change ionic iron (III) coordination compound of Imidazole cation, react simple to operation, product is easily purified, yield is high, this kind of joins Laminate structures is clear and definite, and the most also can stable existence.
Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation the most disclosed by the invention is possible not only to Be catalyzed aromatic aldehyde, aliphatic aldehyde and the oxidative coupling of two grades of amide efficiently, it is also possible to be catalyzed efficiently with aromatic heterocycle aldehyde, Big two grades of amide of steric hindrance are the oxidative coupling of substrate, and catalysis activity and substrate applicability are better than prior art；The catalysis of the present invention Efficiency compared with prior art has clear superiority, and the inventive method solves existing aromatic heterocycle aldehyde, big steric hindrance two grades Amide cannot effectively participate in the problem of this reaction, and the inventive method need not add other parts, and reaction system is simple, tool There is higher Atom economy；Be conducive to industrial applications.
Detailed description of the invention
Below in conjunction with 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
2,6-DIPA (10.0 milliliters, 48 mMs) and triethylamine (7.3 milliliters, 48 mMs) mixing are dissolved in dry In the oxolane of dry mistake, under ice-water bath, it is slowly added dropwise ethyl oxalyl chloride (5.1 milliliters, 48 mMs), drips complete rear chamber The lower stirring of temperature 5 hours.Filtering, filtrate washes three times respectively with dilute hydrochloric acid, saturated aqueous common salt respectively, and organic facies anhydrous sodium sulfate is done Dry 12 hours.Organic facies is concentrated into saturated, adds 100 ml n-hexanes, has solid to separate out, filter, be dried, obtain white solid (N -(diisopropyl phenyl) ethyl oxalate), productivity 92%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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。
WillN(1.31 grams, 12 in the least for-(diisopropyl phenyl) ethyl oxalate (2.78 grams, 10.0 mMs), Ortho-Aminophenol Mole) and triethylamine (2.78 milliliters, 20 mMs) mixing be dissolved in toluene, return stirring 12 hours.It is cooled to room temperature, reaction Liquid is washed three times with dilute hydrochloric acid, saturated common salt respectively, and organic facies anhydrous sodium sulfate is dried 12 hours.Organic facies is concentrated into full With, add 100 ml n-hexanes, have solid to separate out, filter, be dried, obtain white solid (N-(2,6-diisopropyl phenyl)-N '-(2-hydroxy phenyl) oxamides), productivity 85%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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。
TakeN-(2,6-diisopropyl phenyl)-N'-(2-hydroxy phenyl) oxamides (0.74 gram, 2.2 mMs), Xiang Qi In be slowly added to borine tetrahydrofuran solution (17.6 milliliters, 1.0 mol/L, 17.6 mMs) return stirring 12 hours.Cooling To room temperature, it is slowly added dropwise absolute methanol to not having gas to generate, adds concentrated hydrochloric acid (1.5 milliliters, 36%, 18 mM), reactant liquor It is spin-dried for obtaining white solid.In white solid, add ethyl orthoformate (10 milliliters), stir 30 minutes at 90 DEG C, have solid to analyse Going out, filter, filter cake absolute ether is washed three times, is obtained white solid [(Ar1NCH2CH2NAr2) CH] Cl(Ar1=2,6-di-CH (CH3)2-C6H3, Ar2= 2-(OH)-C6H4), productivity 53%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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。
Product is carried out elementary analysis, and result is as follows:
Elementary 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, found that they are at 323.2122 Having a molecular ion peak, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove gained compound For [(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) (0.16 gram, 1.0 in the least to join ferric chloride Mole) tetrahydrofuran solution in, react 4 hours at 30 DEG C, vacuum pumps solvent, and hexane washs, and drains, extracts with oxolane Taking, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, separates out yellowish-brown crystal, productivity 92% under room temperature.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) H:(%) N:(%)
Theoretical value 48.40 5.22 5.38
Actual value 48.31 5.41 5.16
Owing to the coordination compound of ferrum has paramagnetism, so it not being carried out nuclear-magnetism sign.
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeCl4] presented in ion pair, wherein anion portion Divide [FeCl4]-Being characterized by Raman spectrum, it is at 333 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its Having a molecular ion peak at 323.2141, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove 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) add In the tetrahydrofuran solution of ferric bromide (0.30 gram, 1.0 mMs), reacting 16 hours at 45 DEG C, vacuum pumps solvent, oneself Alkane washs, and drains, and extracts with oxolane, and centrifugal clear liquid shifts, and adds hexane recrystallization, separate out reddish brown under room temperature in clear liquid Color crystal, productivity 93%.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) H:(%) N:(%)
Theoretical value 36.09 3.89 4.01
Actual value 36.32 4.15 3.92
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeBr4] presented in ion pair, wherein anionicsite [FeBr4]-Being characterized by Raman spectrum, it is at 204 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its Having a molecular ion peak at 323.2118, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove 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 the synthesis of Cl with reference to the step of embodiment one, utilize 3,5-di-t-butyl-2-hydroxyanilines Replace Ortho-Aminophenol.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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。
Product is carried out elementary analysis, and result is as follows:
Elementary 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, found that they are at 435.3384 Having a molecular ion peak, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove gained compound For [(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) (0.16 gram, 1.0 in the least to join ferric chloride Mole) tetrahydrofuran solution in, react 6 hours at 40 DEG C, vacuum pumps solvent, and hexane washs, and drains, extracts with oxolane Taking, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, separates out yellowish-brown crystal, productivity 85% under room temperature.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) H:(%) N:(%)
Theoretical value 55.00 6.84 4.42
Actual value 55.36 6.53 4.63
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeCl4] presented in ion pair, wherein anionicsite [FeCl4]-Being characterized by Raman spectrum, it is at 333 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its Having a molecular ion peak at 435.3380, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove Gained compound is target compound.
Embodiment four: [(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) add In the tetrahydrofuran solution of ferric bromide (0.30 gram, 1.0 mMs), reacting 20 hours at 60 DEG C, vacuum pumps solvent, oneself Alkane washs, and drains, and extracts with oxolane, and centrifugal clear liquid shifts, and adds hexane recrystallization, separate out reddish brown under room temperature in clear liquid Color crystal, productivity 86%.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) H:(%) N:(%)
Theoretical value 42.94 5.34 3.45
Actual value 43.27 5.46 3.56
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeBr4] presented in ion pair, wherein anionicsite [FeBr4]-Being characterized by Raman spectrum, it is at 204 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its Having a molecular ion peak at 435.3385, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove 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 the synthesis of Cl with reference to the step of embodiment one, utilize 2，4，6-trimethyl aniline to replace 2, 6-diisopropyl aniline；3,5-di-t-butyl-2-hydroxyanilines is utilized to replace Ortho-Aminophenol.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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。
Product is carried out elementary analysis, and result is as follows:
Elementary 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, found that they are at 393.2907 Having a molecular ion peak, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove gained compound For [(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) (0.16 gram, 1.0 in the least to join ferric chloride Mole) tetrahydrofuran solution in, react 2 hours at 60 DEG C, vacuum pumps solvent, and hexane washs, and drains, extracts with oxolane Taking, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, separates out yellowish-brown crystal, productivity 82% under room temperature.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) H:(%) N:(%)
Theoretical value 52.82 6.31 4.74
Actual value 53.11 6.45 5.01
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeCl4] presented in ion pair, wherein anionicsite [FeCl4]-Being characterized by Raman spectrum, it is at 333 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its Having a molecular ion peak at 393.2906, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove 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) add In the tetrahydrofuran solution of ferric bromide (0.30 gram, 1.0 mMs), reacting 10 hours at 70 DEG C, vacuum pumps solvent, oneself Alkane washs, and drains, and extracts with oxolane, and centrifugal clear liquid shifts, and adds hexane recrystallization, separate out reddish brown under room temperature in clear liquid Color crystal, productivity 83%.
Product is carried out elementary analysis, and result is as follows:
Elementary analysis
C:(%) H:(%) N:(%)
Theoretical value 40.61 4.85 3.64
Actual value 40.95 4.95 3.69
This coordination compound [(Ar1NCH2CH2NAr2)CH][FeBr4] presented in ion pair, wherein anionicsite [FeBr4]-Being characterized by Raman spectrum, it is at 204 cm-1There is characteristic peak at place.
The cationic moiety [(Ar of coordination compound1NCH2CH2NAr2)CH]+Characterized by mass spectrum, find its Having a molecular ion peak at 393.2905, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove 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) benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds benzaldehyde (122 Microlitre, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).18 are reacted at 60 DEG C Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is The mixed solvent of 1: 5 is developing solvent), productivity is 85%, and catalytic efficiency is 0.5974g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) o-tolualdehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds o-methyl-benzene first Aldehyde (139 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body Long-pending than be 1: 10 mixed solvent be developing solvent), productivity is 50%, and catalytic efficiency is 0.3708g/mmol/h.The existing skill of this substrate Art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) 4-chloro-benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (12.2 milligrams, 0.015 mM, 3mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 4-chloro-benzaldehyde (168.7 milligrams, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body Long-pending than be 1: 10 mixed solvent be developing solvent), productivity is 93%, and catalytic efficiency is 0.4943g/mmol/h.The existing skill of this substrate Art purifies through column chromatography, and productivity is 61%, and catalytic efficiency is 0.2188g/mmol/h, and this method has bright compared to prior art Aobvious advantage.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) p-bromobenzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds p-bromobenzaldehyde (220.0 milligrams, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C Reacting 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether Volume ratio be the mixed solvent of 1: 20 be developing solvent), productivity is 82%, and catalytic efficiency is 0.3225g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) o-chlorobenzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds o-chlorobenzaldehyde (135 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).React at 80 DEG C 36 hours, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether volume Than be 1: 10 mixed solvent be developing solvent), productivity is 73%, and catalytic efficiency is 0.4029g/mmol/h.This substrate prior art Purifying through column chromatography, productivity is 43%, and catalytic efficiency is 0.3587g/mmol/h, and this method has substantially compared to prior art Advantage.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) 4-Fluorobenzaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 4-Fluorobenzaldehyde (129 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead Answering 36 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body Long-pending than be 1: 20 mixed solvent be developing solvent), productivity is 86%, and catalytic efficiency is 0.1295g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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-naphthaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 1-naphthaldehyde (162 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).36 are reacted at 70 DEG C Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is The mixed solvent of 1: 10 is developing solvent), productivity is 53%, and catalytic efficiency is 0.1784g/mmol/h.This substrate prior art cannot Effectively preparation, this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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 ester that is catalyzed andNThe oxidation of-benzylacetamide is even Connection reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds aldehyde radical benzene first Acid methyl ester (197.1 milligrams, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).? At 60 DEG C react 18 hours, with water terminate reaction, product is extracted with ethyl acetate, column chromatography purify (with ethyl acetate/ Petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 83%, and catalytic efficiency is 0.7170g/mmol/h.This end Thing prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) 2 thiophene carboxaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (20.3 milligrams, 0.025 mM, 5 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 2 thiophene carboxaldehyde (111 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 80 DEG C instead Answering 30 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body Long-pending than be 1: 5 mixed solvent be developing solvent), productivity is 47%, and catalytic efficiency is 0.1122g/mmol/h.The existing skill of this substrate Art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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-thiophenecarboxaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 3-thiophenecarboxaldehyde (106 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body Long-pending than be 1: 10 mixed solvent be developing solvent), productivity is 67%, and catalytic efficiency is 0.1928 g/mmol/h.This substrate is existing Technology cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) 2 furan carboxyaldehyde that is catalyzed andNThe oxidative coupling reaction of-benzylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl Acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 2 furan carboxyaldehyde (99 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).36 are reacted at 60 DEG C Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is The mixed solvent of 1: 10 is developing solvent), productivity is 43%, and catalytic efficiency is 0.2903 g/mmol/h.This substrate prior art without Method is effectively prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) n-hexyl aldehyde that is catalyzed andNThe oxidative coupling reaction of-benzyl phenyl-acetamides
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-benzyl benzene Yl acetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds n-hexyl aldehyde (147 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).At 60 DEG C instead Answering 18 hours, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether body Long-pending than be 1: 20 mixed solvent be developing solvent), productivity is 71%, and catalytic efficiency is 0.6861g/mmol/h.The existing skill of this substrate Art purifies through column chromatography, and productivity is 47%, and catalytic efficiency is that 0.1451g/mmol/h this method has substantially compared to prior art Advantage.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-phenyl-acetamides
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-phenyl Acetamide (67.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds benzaldehyde (122 Microlitre, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).18 are reacted at 60 DEG C Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is The mixed solvent of 1: 5 is developing solvent), productivity is 80%, and catalytic efficiency is 0.5112g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) benzaldehyde that is catalyzed andNThe oxidative coupling reaction of-methylacetamide
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N-methyl Acetamide (36.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds benzaldehyde (122 Microlitre, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).18 are reacted at 60 DEG C Hour, terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies and (with ethyl acetate/petroleum ether volume ratio is The mixed solvent of 1: 10 is developing solvent), productivity is 85%, and catalytic efficiency is 0.4132g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) benzaldehyde that is catalyzed andN-(2,4,6-trimethylphenyl) acetamide Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N -(2,4, 6-trimethylphenyl) acetamide (88.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively Add benzaldehyde (122 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).? At 60 DEG C react 18 hours, with water terminate reaction, product is extracted with ethyl acetate, column chromatography purify (with ethyl acetate/ Petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 97%, and catalytic efficiency is 0.7571g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) benzaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) acetamide Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N -(2,6- Diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively Add benzaldehyde (122 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs). Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with acetic acid second Ester/petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 97%, and catalytic efficiency is 0.8703g/mmol/h. This substrate prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) benzaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) propionic acid amide. Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%),N -(2,6- Diisopropyl phenyl) propionic acid amide. (117.4 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively Add benzaldehyde (122 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).? At 60 DEG C react 18 hours, with water terminate reaction, product is extracted with ethyl acetate, column chromatography purify (with ethyl acetate/ Petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 62%, and catalytic efficiency is 0.5804g/mmol/h.This end Thing prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) and the benzaldehyde that is catalyzed and the oxidative coupling reaction of caprolactam
In reaction bulb, under argon shield, it is sequentially added into catalyst (8.1 milligrams, 0.010 mM, 2 mol%), caprolactam (56.6 milligrams, 0.5 mM), 2.0 milliliter 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).React 24 hours at 70 DEG C, Terminating reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with ethyl acetate/petroleum ether volume ratio for 1: 10 Mixed solvent be developing solvent), productivity is 96%, and catalytic efficiency is 0.4341g/mmol/h.This substrate prior art is through column chromatography Separating, productivity is 67%, and catalytic efficiency is 0.1817g/mmol/h, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) p-tolyl aldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) second The oxidative coupling reaction of amide
In reaction bulb, under argon shield, it is sequentially added into catalyst (16.2 milligrams, 0.020 mM, 4 mol%),N -(2, 6-diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, then depends on Secondary addition p-tolyl aldehyde (142 microlitres, 1.2 mMs), and 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 MM).Reacting 24 hours at 70 DEG C, terminate reaction with water, product is extracted with ethyl acetate, column chromatography purification (with Ethyl acetate/petroleum ether volume ratio be the mixed solvent of 1: 5 be developing solvent), productivity is 89%, and catalytic efficiency is 0.2995g/ mmol/h。
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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-naphthaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) acetamide Oxidative coupling reaction
In reaction bulb, under argon shield, it is sequentially added into catalyst (12.2 milligrams, 0.015 mM, 3 mol%),N -(2,6- Diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stir 2 minutes, more successively Add 1-naphthaldehyde (162 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs). Reacting 28 hours at 80 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with acetic acid second Ester/petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 81%, and catalytic efficiency is 0.4441g/mmol/h. This substrate prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) p-bromobenzaldehyde that is catalyzed andN-(2,6-diisopropyl phenyl) acetyl The oxidative coupling reaction of amine
In reaction bulb, under argon shield, it is sequentially added into catalyst (16.2 milligrams, 0.020 mM, 4 mol%),N -(2, 6-diisopropyl phenyl) acetamide (109.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, then depends on Secondary addition p-bromobenzaldehyde (220.0 milligrams, 1.2 mMs), and 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 MM).Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, column chromatography purification (with Ethyl acetate/petroleum ether volume ratio be the mixed solvent of 1: 10 be developing solvent), productivity is 93%, and catalytic efficiency is 0.5193g/ mmol/h.This substrate prior art cannot effectively be prepared, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing, under room temperature on Unity Inova-400 type NMR instrument measure Characterize: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) coordination compound containing single phenol functionalization Imidazole cation is catalyzed aldehyde and two as single-component catalyst The method of the oxidative coupling reaction of level amide, comprises the following steps: under room temperature, in inert gas atmosphere, successively to reactor Middle addition catalyst, two grades of amide, organic solvents, stirring；Then proceed in reactor, be sequentially added into aldehyde, tert-butyl hydroperoxide Aqueous solution of hydrogen, in 60～80 DEG C of stirring reactions 18～36 hours；Reaction terminates reaction with water after terminating；Product acetic acid second Ester extracts, and is i.e. obtained product by column chromatography, i.e. obtains product；The described ionic iron containing single phenol functionalization Imidazole cation (III) coordination compound has a structural formula of formula I:
Formula I；
Wherein R1For methyl or isopropyl；R2For hydrogen or methyl；R3For hydrogen or the tert-butyl group；X is chlorine or bromine.
Method the most according to claim 1, it is characterised in that: described noble gas is nitrogen or argon；Described organic Solvent is 1,2-dichloroethanes.
Method the most according to claim 1, it is characterised in that: with molar amount, aldehyde: two grades of amide: tert-butyl hydroperoxide Hydrogen: catalyst is 2.4: 1: 2.0: (0.02～0.05)；Response time is 18 hours, and reaction temperature is 60 DEG C.
Method the most according to claim 1, it is characterised in that: with molar amount, aldehyde: two grades of amide: tert-butyl hydroperoxide Hydrogen: catalyst is 2.4: 1: 2.0: 0.02.
Method the most according to claim 1, it is characterised in that: described aldehyde be benzaldehyde, o-tolualdehyde, to chlorobenzene first Aldehyde, p-bromobenzaldehyde, o-chlorobenzaldehyde, 4-Fluorobenzaldehyde, terephthalaldehydic acid methyl ester, 1-naphthaldehyde, 2 thiophene carboxaldehyde, 3-thiophene Fen formaldehyde, 2 furan carboxyaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, just oneself Aldehyde or hutanal；Described two grades of amide areN-benzylacetamide,N-methylacetamide,N-(2,4,6-trimethylphenyl) acetyl Amine,N-(2,6-diisopropyl phenyl) acetamide,N-(2,6-diisopropyl phenyl) propionic acid amide.,N-(4-aminomethyl phenyl) acetyl Amine,N-(4-methoxyphenyl) acetamide,N-(4-chlorphenyl) acetamide,N-(4-trifluoromethyl) acetamide,N-hexamethylene Yl acetamide,N-Phenylpropionamide or caprolactam.
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