CN105001031B - Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation and preparation method and application - Google Patents

Ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation and preparation method and application Download PDF

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CN105001031B
CN105001031B CN201510445241.1A CN201510445241A CN105001031B CN 105001031 B CN105001031 B CN 105001031B CN 201510445241 A CN201510445241 A CN 201510445241A CN 105001031 B CN105001031 B CN 105001031B
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aldehyde
coordination compound
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amide
single phenol
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孙宏枚
吴钰锋
解存飞
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Changshu Intellectual Property Operation Center Co Ltd
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Suzhou University
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Abstract

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

Description

Ionic iron containing single phenol functionalization Imidazole cation (III) Coordination compound and preparation method and application
Technical field
The present invention relates to a kind of metal complex and the application in organic synthesis field thereof, a kind of ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation and preparation method and application.
Background technology
Acid imide is present in many natural products as an important construction unit, is also the resulting structure unit of a lot of medicine, such as: aniracetam, variotin etc..Therefore, build that imide structure is of increased attention (to be seen: Y. J. Wang, C. Y. Chen, Z. Z. the most efficiently 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 often limited by the unstability of carboxylic acid derivates (such as: acyl chlorides) and poor Atom economy.(see C. A. G. N. Montalbetti, V. Falque,Tetrahedron,2005, 61,10827).Along with people's pay attention to day by day to Green Chemistry, the substitute finding carboxylic acid derivates becomes a focus in this research field.
Compared with carboxylic acid derivates, aldehyde compound has the advantage such as metastable chemical property, higher Atom economy, and this makes people start as the succedaneum of carboxylic acid derivates to be incorporated in imido structure.Such as, with NBS (N-bromo-succinimide) as oxidant under conditions of, cuprous bromide can be catalyzed the oxidative coupling of aromatic aldehyde and amide (primary amide and two grades of amide) efficiently and (see L. to generate acid imide Wang, H. Fu, Y. Y. Jiang, Y. F. Zhao,Chem. Eur. J.,2008, 14, 10772)；With tert-butyl hydroperoxide as oxidant, two (triphenylphosphine) Palladium Diacetate can be catalyzed two grades of amide of aromatic aldehyde and pyridine ring modification and carry out oxidative coupling reaction, thus prepares acid imide and (see Y. J. Wang, C. Y. Chen, Z. Z. Huang,Chem. Eur. J.,2013, 19,1129).These results show to replace carboxylic acid derivates to have good application prospect in imido synthesis with aldehyde, but, it is to be overcome that existing method also has some defects to have, such as expensive price, the toxicity etc. of Cu-series catalyst of palladium series catalyst.Therefore, develop inexpensive, low toxicity 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, exploitation Fe-series catalyst be considered as develop the economy and environment-friendly catalyst a Critical policies (Correa, A., Mancheño, O. G., Bolm, C.,Chem. Soc. Rev., 2008, 37,1108).With tert-butyl hydroperoxide as oxidant, the ferrous oxidative coupling that can be catalyzed aromatic aldehyde, fatty aldehyde and two grades of amide of dibrominated carrys out synthesizing imide and (sees J. Wang, C. Liu, J. W. Yuan, A. W. Lei,Chem. Commun.,2014, 50, 4736).The method can be catalyzed the oxidative coupling of aldehyde and two grades of amide to prepare acid imide, but there is obvious drawback, mainly has: (1) dibrominated ferrous iron is unstable, the most easily oxidation, deliquescence, operation inconvenience；(2) purity of these iron salt is often mixed with other metal (such as copper) of denier by its commercial source difference thus causes the instability of catalytic performance；(3) substrate applicability need to expand further, as due to reasons such as the steric hindrance of aromatic heterocycle aldehyde hetero atom and metal-complexing and big two grades of amide of steric hindrance are bigger, caused these substrates cannot effectively carry out above-mentioned reaction.
In present inventor's research work previously, once design has synthesized ionic iron (III) coordination compound containing bisphenol functionalized imidazoles (quinoline) cation, finds that they (can see: (1) C. with the cross-coupling reaction of effective catalyst aryl grignard reagent and the halogenated alkyl hydrocarbon containing b-H 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, yet there are no ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation and the report of the oxidative coupling reaction being catalyzed between aldehyde and two grades of amide thereof.
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, the oxidative coupling being possible not only to be catalyzed efficiently aromatic aldehyde, aliphatic aldehyde and two grades of amide carrys out synthesizing imide, the oxidative coupling reaction that can participate in efficient catalytic aromatic heterocycle aldehyde and big two grades of amide of steric hindrance, its catalysis activity and substrate applicability are 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 carries out the application of oxidative coupling reaction as single-component catalyst catalysis aldehyde and two grades of amide；
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 prior art, 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 single-component catalyst catalysis aldehyde and the method for the oxidative coupling reaction of two grades of amide, comprise the following steps: under room temperature, in inert gas atmosphere, catalyst, two grades of amide, organic solvents, stirring is added successively in reactor；Then proceed in reactor, be sequentially added into 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, and i.e. obtains product by column chromatography (with ethyl acetate/petroleum ether volume ratio for 1: the mixed solvent of (5～20) is as developing solvent).
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, and wherein 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 amide are 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: benzaldehyde, o-tolualdehyde, 4-chloro-benzaldehyde, o-chlorobenzaldehyde, p-bromobenzaldehyde, 4-Fluorobenzaldehyde, p-tolyl aldehyde, 1-naphthaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, terephthalaldehydic acid methyl ester etc.；Described fatty aldehyde is the aldehyde compound with open chain alkane framing structure, such as: n-hexyl aldehyde, hutanal etc.；Described aromatic heterocycle aldehyde is the aldehyde compound with aromatic heterocycle framing structure, such as: 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde or 2 furan carboxyaldehyde etc.；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-diisopropyl 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, and the consumption of tert-butyl hydroperoxide 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, and reaction temperature 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, the chemical general formula of described 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, R2One in hydrogen atom, methyl, 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 is ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation, and 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, comprise the following steps: under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, iron salt system is dissolved in solvent with single phenol functionalization imidazoline villaumite, reacts 2～20 hours at 30～70 DEG C；Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, removes precipitation, is recrystallized to give ferrum (III) coordination compound with the mixed solvent of hexane and oxolane；Described iron salt system is ferric bromide and 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 solvent with single phenol functionalization imidazoline villaumite, reacts 2～6 hours at 30～60 DEG C；Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, removes precipitation, is recrystallized to give ferrum (III) coordination compound with the mixed solvent of hexane and oxolane, is ferrum (III) coordination compound of above-mentioned ion-type.
In technique scheme, described noble gas is nitrogen or argon, and in the mixed solvent of described hexane and oxolane, 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 oxolane, and 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, ferric bromide, single phenol functionalization imidazoline villaumite and sodium bromide are dissolved in solvent, react 10～20 hours at 45～70 DEG C；Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, removes precipitation, is recrystallized to give ferrum (III) coordination compound with the mixed solvent of oxolane and hexane, is above-mentioned ionic iron (III) coordination compound.
In technique scheme, described noble gas is nitrogen or argon, and in the mixed solvent of described hexane and oxolane, 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, and 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 realize the flexible modulation of the sterically hindered and electronic effect to corresponding ferrum (III) coordination compound by the phenol epoxide and alkyl introducing different structure on two nitrogen-atoms of imidazoline ring respectively, thus develops the Fe-series catalyst that a class is new and effective.
2. the present invention prepares ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation by iron salt system and the reaction at ambient pressure of single phenol functionalization imidazoline villaumite, react simple to operation, product is easily purified, yield high, this kind of complex structure 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, can also be catalyzed with aromatic heterocycle aldehyde, the two grades of amide of the big steric hindrance oxidative coupling as substrate efficiently, catalysis activity and substrate applicability are better than prior art；The catalytic efficiency of the present invention compared with prior art has clear superiority, and the problem that the inventive method solves existing aromatic heterocycle aldehyde, two grades of amide of big steric hindrance cannot effectively participate in this reaction, and the inventive method need not add other parts, reaction system is simple, has 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
By 2,6-DIPA (10.0 milliliters, 48 mMs) and triethylamine (7.3 milliliters, 48 mMs) mixing be dissolved in dried oxolane, under ice-water bath, be slowly added dropwise ethyl oxalyl chloride (5.1 milliliters, 48 mMs), drip and stir 5 hours under complete rear chamber temperature.Filtering, filtrate is washed three times respectively with dilute hydrochloric acid, saturated aqueous common salt respectively, and organic facies anhydrous sodium sulfate is dried 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, measure on Unity Inova-400 type NMR instrument under room temperature and 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-(diisopropyl phenyl) ethyl oxalate (2.78 grams, 10.0 mMs), Ortho-Aminophenol (1.31 grams, 12 mMs) and triethylamine (2.78 milliliters, 20 mMs) mixing are dissolved in toluene, return stirring 12 hours.Being cooled to room temperature, reactant liquor 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 saturated, adds 100 ml n-hexanes, has 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, measure on Unity Inova-400 type NMR instrument under room temperature and 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), it is slowly added to borine tetrahydrofuran solution (17.6 milliliters, 1.0 mol/L, 17.6 mMs) return stirring wherein 12 hours.Being cooled to room temperature, be slowly added dropwise absolute methanol to not having gas to generate, add concentrated hydrochloric acid (1.5 milliliters, 36%, 18 mM), reactant liquor is spin-dried for obtaining white solid.Adding ethyl orthoformate (10 milliliters) in white solid, stir 30 minutes, have solid to separate out at 90 DEG C, 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, measure on Unity Inova-400 type NMR instrument under room temperature and 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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 323.2122, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove that 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) join in the tetrahydrofuran solution of ferric chloride (0.16 gram, 1.0 mMs), react 4 hours at 30 DEG C, vacuum pumps solvent, hexane washs, and drains, extracts with oxolane, centrifugal clear liquid shifts, in clear liquid, add hexane recrystallization, under room temperature, separate out yellowish-brown crystal, productivity 92%.
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 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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 323.2141, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove that 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) join ferric bromide (0.30 gram, 1.0 mMs) tetrahydrofuran solution in, reacting 16 hours at 45 DEG C, vacuum pumps solvent, and hexane washs, drain, extracting with oxolane, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, red-brown crystals, productivity 93% is separated out under room temperature.
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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 323.2118, this molecular ion peak is 323.21 in theory, and actual measurement substantially conforms to theory.Prove that 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 replaces Ortho-Aminophenol.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 435.3384, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove that 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) join in the tetrahydrofuran solution of ferric chloride (0.16 gram, 1.0 mMs), react 6 hours at 40 DEG C, vacuum pumps solvent, hexane washs, and drains, extracts with oxolane, centrifugal clear liquid shifts, in clear liquid, add hexane recrystallization, under room temperature, separate out yellowish-brown crystal, productivity 85%.
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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 435.3380, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove that 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) join ferric bromide (0.30 gram, 1.0 mMs) tetrahydrofuran solution in, reacting 20 hours at 60 DEG C, vacuum pumps solvent, and hexane washs, drain, extracting with oxolane, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, red-brown crystals, productivity 86% is separated out under room temperature.
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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 435.3385, this molecular ion peak is 435.34 in theory, and actual measurement substantially conforms to theory.Prove that 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-DIPA；3,5-di-t-butyl-2-hydroxyanilines is utilized to replace Ortho-Aminophenol.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 393.2907, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove that 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) join in the tetrahydrofuran solution of ferric chloride (0.16 gram, 1.0 mMs), react 2 hours at 60 DEG C, vacuum pumps solvent, hexane washs, and drains, extracts with oxolane, centrifugal clear liquid shifts, in clear liquid, add hexane recrystallization, under room temperature, separate out yellowish-brown crystal, productivity 82%.
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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 393.2906, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove that 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) join ferric bromide (0.30 gram, 1.0 mMs) tetrahydrofuran solution in, reacting 10 hours at 70 DEG C, vacuum pumps solvent, and hexane washs, drain, extracting with oxolane, centrifugal clear liquid shifts, and adds hexane recrystallization in clear liquid, red-brown crystals, productivity 83% is separated out under room temperature.
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]+Being characterized by mass spectrum, find that it has a molecular ion peak at 393.2905, this molecular ion peak is 393.29 in theory, and actual measurement substantially conforms to theory.Prove that 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-benzylacetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 5 as developing solvent), and productivity is 85%, and catalytic efficiency is 0.5974g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds o-tolualdehyde (139 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 50%, and catalytic efficiency is 0.3708g/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, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 93%, and catalytic efficiency is 0.4943g/mmol/h.This substrate prior art purifies through column chromatography, and productivity is 61%, and catalytic efficiency is 0.2188g/mmol/h, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 20 as developing solvent), and productivity is 82%, and catalytic efficiency is 0.3225g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 36 hours at 80 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 73%, and catalytic efficiency is 0.4029g/mmol/h.This substrate prior art purifies through column chromatography, and productivity is 43%, and catalytic efficiency is 0.3587g/mmol/h, and this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 36 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 20 as developing solvent), and productivity is 86%, and catalytic efficiency is 0.1295g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 36 hours at 70 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 53%, and catalytic efficiency is 0.1784g/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, measure on Unity Inova-400 type NMR instrument under room temperature and 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 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-benzylacetamide (74.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds terephthalaldehydic acid methyl ester (197.1 milligrams, 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 83%, and catalytic efficiency is 0.7170g/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, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 30 hours at 80 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 5 as developing solvent), and productivity is 47%, and catalytic efficiency is 0.1122g/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, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 67%, and catalytic efficiency is 0.1928 g/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, measure on Unity Inova-400 type NMR instrument under room temperature and 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-benzylacetamide (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).Reacting 36 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 43%, and catalytic efficiency is 0.2903 g/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, measure on Unity Inova-400 type NMR instrument under room temperature and 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 phenyl-acetamides (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).Reacting 18 hours at 60 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 20 as developing solvent), and productivity is 71%, and catalytic efficiency is 0.6861g/mmol/h.This substrate prior art purifies through column chromatography, and productivity is 47%, and catalytic efficiency is that 0.1451g/mmol/h this method has clear superiority compared to prior art.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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-acetamides (67.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 5 as developing solvent), and productivity is 80%, and catalytic efficiency is 0.5112g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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-methylacetamide (36.5 milligrams, 0.5 mM), 2.0 milliliter 1,2-dichloroethanes, stirs 2 minutes, sequentially adds 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 85%, and catalytic efficiency is 0.4132g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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 andNThe oxidative coupling reaction of-(2,4,6-trimethylphenyl) acetamide
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, stirs 2 minutes, sequentially adds 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 97%, and catalytic efficiency is 0.7571g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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 andNThe oxidative coupling reaction of-(2,6-diisopropyl phenyl) acetamide
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, stirs 2 minutes, sequentially adds 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and 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, measure on Unity Inova-400 type NMR instrument under room temperature and 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 andNThe oxidative coupling reaction of-(2,6-diisopropyl phenyl) propionic acid amide.
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, stirs 2 minutes, sequentially adds 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 62%, and catalytic efficiency is 0.5804g/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, measure on Unity Inova-400 type NMR instrument under room temperature and 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, be sequentially added under argon shield 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).Reacting 24 hours at 70 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and productivity is 96%, and catalytic efficiency is 0.4341g/mmol/h.This substrate prior art is through column chromatography for separation, and 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, measure on Unity Inova-400 type NMR instrument under room temperature and 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 andNThe oxidative coupling reaction of-(2,6-diisopropyl phenyl) acetamide
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, sequentially adds p-tolyl aldehyde (142 microlitres, 1.2 mMs), 70% tert-butyl hydroperoxide aqueous solution (136 microlitres, 1.0 mMs).Reacting 24 hours at 70 DEG C, terminate reaction with water, product is extracted with ethyl acetate, and column chromatography purifies (with mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 5 as developing solvent), and productivity is 89%, and catalytic efficiency is 0.2995g/mmol/h.
Product is dissolved in CDCl3In (about 0.4 ML), tube sealing, measure on Unity Inova-400 type NMR instrument under room temperature and 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 andNThe oxidative coupling reaction of-(2,6-diisopropyl phenyl) acetamide
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, stirs 2 minutes, sequentially adds 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and 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, measure on Unity Inova-400 type NMR instrument under room temperature and 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 andNThe oxidative coupling reaction of-(2,6-diisopropyl phenyl) acetamide
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, sequentially adds p-bromobenzaldehyde (220.0 milligrams, 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 mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 10 as developing solvent), and 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, measure on Unity Inova-400 type NMR instrument under room temperature and 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 (6)

1. ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation carries out the application of oxidative coupling reaction as single-component catalyst catalysis aldehyde and two grades of amide；Described ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation 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；
Described aldehyde is aromatic aldehyde, fatty aldehyde or aromatic heterocycle aldehyde；Two grades of amide are chain amide or lactams.
Application the most according to claim 1, it is characterised in that: catalyst amount is the 2%～5% of two grades of amide moles.
Application the most according to claim 1, it is characterised in that: described aldehyde be benzaldehyde, o-tolualdehyde, 4-chloro-benzaldehyde, p-bromobenzaldehyde, o-chlorobenzaldehyde, 4-Fluorobenzaldehyde, terephthalaldehydic acid methyl ester, 1-naphthaldehyde, 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde, 2 furan carboxyaldehyde, p-tolyl aldehyde, P-methoxybenzal-dehyde, paranitrobenzaldehyde, to cyanobenzaldehyde, n-hexyl aldehyde or hutanal；Described two grades of amide areN-benzylacetamide,N-methylacetamide,N-(2,4,6-trimethylphenyl) acetamide,N-(2,6-diisopropyl phenyl) acetamide,N-(2,6-diisopropyl 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 or caprolactam.
4., containing ionic iron (III) coordination compound for single phenol functionalization Imidazole cation, described ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation 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.
5. described in claim 4, contain the preparation method of ionic iron (III) coordination compound of single phenol functionalization Imidazole cation, it is characterized in that, comprise the following steps: under the conditions of anhydrous and oxygen-free, in inert gas atmosphere, iron salt system is dissolved in solvent with single phenol functionalization imidazoline villaumite, reacts 2～20 hours at 30～70 DEG C；Solvent removed in vacuo, extracts residue with tetrahydrofuran solvent, removes precipitation, is recrystallized to give described ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation with the mixed solvent of hexane and oxolane；Described iron salt system is ferric bromide and the mixture of sodium bromide or ferric chloride；In the mixed solvent of described hexane and oxolane, the volume ratio of hexane and oxolane is 1: (4～15).
The preparation method of ionic iron (III) coordination compound containing single phenol functionalization Imidazole cation the most according to claim 5, it is characterized in that: when the mixture that iron salt system is ferric bromide and sodium bromide, the mol ratio of ferric bromide, single phenol functionalization imidazoline villaumite and sodium bromide is 1: 1: 6, solvent is oxolane, reaction temperature is 45～70 DEG C, and the response time is 10～20 hours；When iron salt system is ferric chloride, ferric chloride is 1: 1 with the mol ratio of single phenol functionalization imidazoline villaumite, and solvent is oxolane, and reaction temperature is 30～60 DEG C, and the response time is 2～6 hours.
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