CN102887923A - Ionic iron (III) complex containing bisphenol functional imidazoline salt and application thereof - Google Patents
Ionic iron (III) complex containing bisphenol functional imidazoline salt and application thereof Download PDFInfo
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Abstract
The invention discloses an ionic iron (III) complex containing bisphenol functional imidazoline salt, which is expressed by the following chemical structural formula shown in the specification, wherein R1 and R2 are respectively one of hydrogen atom, methyl and tert-butyl; and X is one of chlorine or bromine. According to the ionic iron (III) complex containing bisphenol functional imidazoline salt, such structural unit as imidazoline is first introduced into the design and synthesis of a ligand; meanwhile, the flexible and variable regulation and control on the steric hindrance and electronic effect of the corresponding iron (III) complex is realized by introducing a structure-variable phenoxy modification radical onto the imidazoline ring, thus developing a novel efficient iron-based catalyst; and the cross coupling reaction of alkyl primary/secondary bromohydrocarbon and alkyl primary/secondary chlorohydrocarbon can be effectively catalyzed.
Description
Technical field
The present invention relates to a kind of metal complexes, be specifically related to a kind of ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt and as single component catalyst at aryl grignard reagent with contain application in the cross-coupling reaction between the halogenated alkyl hydrocarbon of b-H.
Background technology
The Kumada cross-coupling reaction of transition metal complex catalysis is that one of most important method that makes up in the organic synthesis C-C is (referring to de Meijere, A.; Diederich, F., Eds.; Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; Wiley-VCH, Weinheim, 2004), develop efficient new catalyst is the core impellent of this field development always.In this reaction, traditional effective catalyst mostly is greatly palladium system or nickel is title complex.Last decade comes, and along with the intensification of people to chemical industry Sustainable development understanding, Fe-series catalyst has cheapness, low toxicity, the characteristics such as efficient because of it, particularly can eliminate reaction and receive increasing concern by establishment β-H.Some Fe-series catalysts be owing to can effectively suppress β-H and eliminates reaction, thereby but catalysis contains the linked reaction of the halogenated alkyl hydrocarbon participation of β-H (namely relates to sp
3Hydridization carbon atom and sp
2, linked reaction between sp hydridization carbon atom) (referring to Sherry, B. D.; F ü rstner, A.; Acc. Chem. Res., 2008,41,1500).Therefore, the exploitation Fe-series catalyst is considered to develop more economical a, Critical policies of environment-friendly catalyst more.
At aryl grignard reagent with contain in the cross-coupling reaction between the halogenated alkyl hydrocarbon of β-H, the iron of exploitation is that catalyst system roughly can be divided into two large classes at present, and a class is (such as FeCl by simple molysite
3) and assistant ligand (such as phosphine part, organic amine) composition, another kind of is the iron complex with clear and definite structure.
The catalyst system of the first kind as, document Nakamura, M.; Matsuo, K.; Ito, S.; Nakamura, E. J. Am. Chem. Soc. 2004, reported in 126,3686 with iron trichloride and Tetramethyl Ethylene Diamine (TMEDA) as catalyst system catalysis aryl grignard reagent and the alkyl primary of a series of b-H of containing, the cross-coupling reaction of secondary halohydrocarbon.
Its advantage is that catalyzer simply is easy to get, but also has some obvious drawbacks, mainly is: (1) FeCl
3Etc. simple molysite deliquescence very easily, operation inconvenience; (2) FeCl
3Be subjected to its commercial source difference to tend to be mixed with other metal (such as copper) of denier etc. the purity of simple molysite thus cause the unstable of catalytic performance; (3) use of excess ligand, rate of feeding is excessively slow (referring to (1) Cahiez, G.; Habiak, V.; Duplais, C.; Moyeux, A. Angew. Chem. Int. Ed., 2007,46,23,4364; (2) Buchwald, S. L.; Bolm, C. Angew. Chem. Int. Ed., 2009,48,31,5586).
Therefore, the research and development that have an iron complex of clear and definite structure become a approach the most effective that this class catalyzer is optimized and expands gradually (referring to Noda, D.; Sunada, Y.; Hatakeyama, T.; Nakamura, M.; Nagashima, H. J. Am. Chem. Soc., 2009,131,6078).
For example, the people such as Gaertner in 2006 find that ionic iron (III) title complex that contains alkyl substituted imidazole salt has good catalytic activity, its reaction conditions is: the Grignard reagent consumption is 1.5 times of halohydrocarbon, catalyst levels is 5 mol% of halohydrocarbon, reaction is 10 minutes in ether, and temperature is 0 ℃, and the productive rate of p-methylphenyl magnesium bromide and bromocyclohexane cross-coupling product is 89%, catalytic efficiency is 18.61 g/mmol/h(referring to Bica, K.; Gaertner, P. Org. Lett., 2006,8,733); But the people such as Kozak in 2011 have reported the two fragrant oxygen iron (III) of amine bridging a series of aryl grignard reagents of title complex catalysis and contain cross-coupling reaction between the halogenated alkyl hydrocarbon of b-H, its reaction conditions is: the Grignard reagent consumption is 2 times of halohydrocarbon, catalyst levels is 5 mol% of halohydrocarbon, reaction is 30 minutes in ether, temperature is 22 ℃, the productive rate of phenyl-magnesium-bromide and bromocyclohexane cross-coupling product is greater than 95%, and catalytic efficiency is 6.08 g/mmol/h(referring to Qian, X.; Dawe, L. N.; Kozak, C. M. Dalton Trans., 2011,40,933).
Chinese invention patent CN101671370A discloses contriver place seminar and has designed ionic iron (III) title complex that a synthetic class contains bisphenol functionalized imidazole, find that it has high catalytic activity to aryl grignard reagent and the cross-coupling reaction that contains between the halogenated alkyl hydrocarbon of b-H, its reaction conditions is: the Grignard reagent consumption is 1.2 times of halohydrocarbon, catalyst levels is 1 mol% of halohydrocarbon, reaction is 30 minutes in ether, temperature is 30 ℃, the productive rate of p-methylphenyl magnesium bromide and bromocyclohexane cross-coupling product is 94%, and catalytic efficiency is up to 32.71 g/mmol/h.Chinese invention patent application CN101928251A discloses synthetic a kind of ionic iron (III) title complex that contains nitrogen-bridged bisphenol functionalized imidazole of contriver place seminar design, it also has preferably catalytic activity to above-mentioned cross-coupling reaction, its reaction conditions is: the Grignard reagent consumption is 1.2 times of halohydrocarbon, catalyst levels is 2 mol% of halohydrocarbon, reaction is 30 minutes in ether, temperature is 25 ℃, the productive rate of p-methylphenyl magnesium bromide and bromocyclohexane cross-coupling product is 97%, and catalytic efficiency is 16.88 g/mmol/h.Chinese invention patent application 102603806A discloses synthetic a kind of ionic iron (III) title complex that contains phenol bridging Neo Heliopan AP of contriver place seminar design, it has high catalytic activity to above-mentioned cross-coupling reaction, its reaction conditions is: the Grignard reagent consumption is 1.2 times of halohydrocarbon, catalyst levels is 1 mol%, reaction is 20 minutes in ether, temperature is 25 ℃, the productive rate of p-methylphenyl magnesium bromide and bromocyclohexane cross-coupling product is 99%, and catalytic efficiency is 51.68 g/mmol/h.
What is particularly worth mentioning is that: in above-mentioned cross-coupling reaction, if can will have higher commercial application prospect as reaction substrate with the alkyl hydrochloric ether, because compare for hydrocarbon phase with alkyl bromide, the alkyl hydrochloric ether has obvious price advantage and diversity.But, in the Fe-series catalyst of above-mentioned exploitation effectively catalysis contain the cross-coupling reaction that the alkyl hydrochloric ether of b-H participates in successful example seldom, the side reactions such as dehalogenation easily occur in the alkyl hydrochloric ether in coupling reaction process, the yield of target product is generally on the low side.For example, in above-mentioned cross-coupling reaction, if replace bromocyclohexane with chlorocyclohexane, the yield of target product will be reduced to 75%(referring to Bica, K. from 89%; Gaertner, P. Org. Lett. 2006,8,733), perhaps lower 47%(referring to Qian, X.; Dawe, L. N.; Kozak, C. M. Dalton Trans., 2011,40,933).Therefore the synthetic cross-coupling reaction that the alkyl hydrochloric ether is participated in of design still has the catalyzer of greater activity to have significant application value.
Summary of the invention
Goal of the invention of the present invention provides a kind of ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt, the utmost point efficiently the catalysis aryl grignard reagent and contain cross-coupling reaction between the alkyl hydrobromic ether of b-H in, the effective cross-coupling reaction that participates in of catalysis alkyl hydrochloric ether.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt, and the iron of described ionic (III) title complex is expressed by the following chemical structure formula:
, in the formula, R
1And R
2Be selected from respectively a kind of in hydrogen atom, methyl, the tertiary butyl, X is a kind of in the chlorine or bromine.
In the technique scheme, the iron of described ionic (III) title complex is iron (III) title complex that contains bisphenol functionalized imidazoline salt, and the synthetic method of bisphenol functionalized imidazoline salt part is prior art, referring to: (1) Kil, S. M., Thomas, W., Eberhard, B., K. W. Inorg. Chem., 2004,43,2922; (2) Geert, J. M., Meppelder; Fan, H. T., Spaniol, T. P., Jun, O. Organometallics, 2009,28,5159; (3) Charles, R.; Lydia, B.; Stephane, B. L.; Samuel, D. Organometallics, 2010,29,1191; (4) David, R. W.; Nilay, H.; Jay, A. L.; John, E. B. Organometallics, 2010,29,1; (5) Laure, B.; Edith, C.; Guy, L.; Stephane, B. L.; Vincent, C. Chem. Rev., 2011,111,2705.
When X was chlorine, the method for preparing iron (III) title complex of above-mentioned ionic may further comprise the steps:
[1] under the anhydrous and oxygen-free condition, in inert gas atmosphere, iron trichloride and bisphenol functionalized imidazoline salt are dissolved in the solvent, in 20～60 ℃ of lower reactions 1～6 hour;
[2] solvent removed in vacuo with tetrahydrofuran solvent extraction residuum, is removed precipitation, obtains iron (III) title complex with the mixed solvent recrystallization of hexane and tetrahydrofuran (THF), is iron (III) title complex of above-mentioned ionic.
In the technique scheme, described rare gas element is nitrogen or argon gas, and the volume ratio of hexane and tetrahydrofuran (THF) is 1:4～1:15 in the mixed solvent of described hexane and tetrahydrofuran (THF).
In the preferred technical scheme, the mol ratio of iron trichloride and bisphenol functionalized tetrahydroglyoxaline villaumite is 1:1, and solvent is tetrahydrofuran (THF), and temperature of reaction is 30 ℃, and the reaction times is 2 hours.
When X was bromine, the method for preparing iron (III) title complex of above-mentioned ionic may further comprise the steps:
[1] under the anhydrous and oxygen-free condition, in inert gas atmosphere, ferric bromide, bisphenol functionalized tetrahydroglyoxaline villaumite and Sodium Bromide are dissolved in the solvent, in 30～65 ℃ of lower reactions 6～24 hours;
[2] solvent removed in vacuo with tetrahydrofuran solvent extraction residuum, is removed precipitation, obtains iron (III) title complex with the mixed solvent recrystallization of tetrahydrofuran (THF) and hexane, is iron (III) title complex of above-mentioned ionic.
In the technique scheme, described rare gas element is nitrogen or argon gas, and the volume ratio of hexane and tetrahydrofuran (THF) is 1:4～1:15 in the mixed solvent of described hexane and tetrahydrofuran (THF).
In the preferred technical scheme, ferric bromide, the mol ratio of bisphenol functionalized tetrahydroglyoxaline villaumite and Sodium Bromide is 1:1:3, and solvent is tetrahydrofuran (THF), and temperature of reaction is 60 ℃, and the reaction times is 12 hours.
In the technique scheme, the selection of described solvent is according to being:
[1] can dissolve ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt;
[2] do not contain active hydrogen,
For example: tetrahydrofuran (THF), methylene dichloride.
The present invention protects iron (III) title complex of above-mentioned ionic to carry out the application of cross-coupling reaction as single-component catalyst catalysis aryl grignard reagent and the halogenated alkyl hydrocarbon that contains b-H simultaneously.
The iron of above-mentioned ionic (III) title complex carries out the method for cross-coupling reaction as single component catalyst catalysis aryl grignard reagent and the halogenated alkyl hydrocarbon that contains b-H, may further comprise the steps:
[1] under the anhydrous and oxygen-free condition, in inert gas atmosphere, adds successively the diethyl ether solution of catalyzer, halogenated alkyl hydrocarbon, solvent ether, aryl grignard reagent;
[2] 0～45 ℃ of stirring reaction 10～60 minutes, with the aqueous solution termination reaction of saturated ammonium chloride;
[3] reaction product ethyl acetate extraction, separating-purifying.
In the technique scheme, described rare gas element is nitrogen or argon gas.
In the preferred technical scheme, when halohydrocarbon was the alkyl hydrobromic ether, in amount of substance, the Grignard reagent consumption was 1.2 times of halohydrocarbon, and catalyst levels is 1 mol% of halohydrocarbon, and reaction is 15 minutes in ether, and temperature is 30 ℃; When halohydrocarbon was the alkyl hydrochloric ether, in amount of substance, the Grignard reagent consumption was 1.5 times of halohydrocarbon, and catalyst levels is 5 mol% of halohydrocarbon, and reaction is 40 minutes in ether, and temperature is 25 ℃.
In the technique scheme, product can be purified by column chromatography for separation.
For detecting yield, in the step [1], after adding the halogenated alkyl hydrocarbon, add again n-hexadecane, in the step [3], behind the ethyl acetate extraction, do interior mark with n-hexadecane, by the yield of gas Chromatographic Determination product.
Principle of the present invention is: described ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt in reaction process by with the effect of Grignard reagent, but in-situ transesterification becomes the stable lower valency ironwork intermediate of saturated N-heterocyclic carbine of being modified by the phenol negative oxygen ion, thus make described contain the ionic iron (III) of bisphenol functionalized imidazoline salt but title complex changes the catalyzer of efficient catalytic cross-coupling reaction at the reaction system situ.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. during ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt of the present invention synthesizes the design of this structural unit introducing part of tetrahydroglyoxaline first, modify base and realize the regulating and control of the sterically hindered and electronic effect of corresponding iron (III) title complex flexible and changeablely by introduce the changeable phenol oxygen of structure at the tetrahydroglyoxaline ring simultaneously, thereby develop the new and effective Fe-series catalyst of a class;
2. the present invention prepares the iron that contains bisphenol functionalized imidazoline salt (III) title complex of ionic in the reaction under the atmospheric pressure at room by three iron halide and bisphenol functionalized imidazoline salt, react simple to operation, product is easily purified, yield is high, but and in air also stable existence.
Ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt of the present invention not only to aryl grignard reagent and contain the alkyl primary of β-H, the cross-coupling reaction between the secondary hydrobromic ether has high catalytic activity, with the iron of having reported at present be that the high catalytic activity of catalyst system is equal or higher; And the effective cross-coupling reaction that participates in of catalysis alkyl primary, secondary hydrochloric ether, catalytic selectivity (ability that namely suppresses the side reactions such as hydrochloric ether generation dehalogenation) is better than bibliographical information.Thereby low this problem of cross-coupling reaction yield that contains the alkyl hydrochloric ether participation of β-H for catalysis in the solution prior art provides a new strategy and method.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment one:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, X's=Cl) is synthetic.
Part synthetic referring to Charles, R.; Lydia, B.; Stephane, B. L.; Samuel, D. Organometallics, 2010,29,1191.
With [(ArNCH
2CH
2NAr) CH] the Cl(0.52 gram, 1.0 mmole) join in the tetrahydrofuran solution of iron trichloride (0.16 gram, 1.0 mmoles) 30 ℃ of lower reactions 2 hours, vacuum is taken out desolventizing, the hexane washing is drained, and extracts with tetrahydrofuran (THF), centrifugal clear liquid shifts, in clear liquid, add the hexane recrystallization, separate out the yellowish brown crystal under the room temperature, productive rate 88%.
Product is carried out ultimate analysis, the test fusing point, the result is as follows:
Ultimate analysis and fusing point
| ? | C：（%） | H：（%） | N：（%） |
| Theoretical value | 54.97 | 6.99 | 4.14 |
| Actual value | 54.55 | 7.19 | 3.91 |
Because the title complex of iron has paramagnetism, characterize so it is not carried out nuclear-magnetism.
This title complex [(ArNCH
2CH
2NAr) CH] FeCl
4That form with ion pair exists, [FeCl wherein
4]
-Characterize by Raman spectrum, find that it is at 333 cm
-1There is characteristic peak at the place, with bibliographical information (Melissa, S. S.; Eric, R. S.; Eric, V. P.; Freeman, R. G. Inorg. Chem. 2001,40,2298) be consistent.
The cationic moiety [(ArNCH of title complex
2CH
2NAr) CH]
+Characterize by mass spectrum, find that it has a molecular ion peak at 479.3647 places, this molecular ion peak is 479.36 in theory, and actual measurement meets substantially with theory.
Proof gained compound is target compound.
Embodiment two:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, X's=Br) is synthetic.
Successively with [(ArNCH
2CH
2NAr) CH] the Cl(0.52 gram, 1.0 mmoles) and the NaBr(0.32 gram, 3.0 mmoles) (0.29 restrains to join ferric bromide, 1.0 in tetrahydrofuran solution mmole), 60 ℃ of lower reactions 12 hours, vacuum is taken out desolventizing, the hexane washing, drain, with the tetrahydrofuran (THF) extraction, centrifugal clear liquid shifts, and adds the hexane recrystallization in clear liquid, separate out the reddish-brown crystal under the room temperature, productive rate 80%.
Product is carried out ultimate analysis, the test fusing point, the result is as follows:
Ultimate analysis and fusing point
| ? | C：（%） | H：（%） | N：（%） |
| Theoretical value | 43.54 | 5.54 | 3.28 |
| Actual value | 44.05 | 5.95 | 3.25 |
Because the title complex of iron has paramagnetism, characterize so it is not carried out nuclear-magnetism.
This title complex [(ArNCH
2CH
2NAr) CH] FeBr
4That form with ion pair exists, [FeBr wherein
4]
-Characterize by Raman spectrum, find that it is at 204 cm
-1There is characteristic peak at the place, with bibliographical information (Melissa, S. S.; Eric, R. S.; Eric, V. P.; Freeman, R. G. Inorg. Chem. 2001,40,2298) be consistent.
The cationic moiety [(ArNCH of title complex
2CH
2NAr) CH]
+Characterize by mass spectrum, find that it has a molecular ion peak at 479.3647 places, this molecular ion peak is 479.36 in theory, and actual measurement meets substantially with theory.
Proof gained compound is target compound.
Embodiment three:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=5-C (CH
3)
3-2-(OH)-C
6H
3, X's=Cl) is synthetic
(part synthetic referring to David, R. W.; Nilay, H.; Jay, A. L.; John, E. B. Organometallics, 2010,29,1).
With [(ArNCH
2CH
2NAr) CH] the Cl(0.40 gram, 1.0 mmole) join in the tetrahydrofuran solution of iron trichloride (0.16 gram, 1.0 mmoles) 30 ℃ of lower reactions 2 hours, vacuum is taken out desolventizing, the hexane washing is drained, and extracts with tetrahydrofuran (THF), centrifugal clear liquid shifts, in clear liquid, add the hexane recrystallization, separate out brown crystal under the room temperature, productive rate 84%.
Product is carried out ultimate analysis, and the result is as follows:
Ultimate analysis
| ? | C：（%） | H：（%） | N：（%） |
| Theoretical value | 48.88 | 5.53 | 4.96 |
| Actual value | 49.22 | 5.61 | 4.90 |
Because the title complex of iron has paramagnetism, characterize so it is not carried out nuclear-magnetism.
This title complex [(ArNCH
2CH
2NAr) CH] FeCl
4That form with ion pair exists, [FeCl wherein
4]
-Characterize by Raman spectrum, find that it is at 333 cm
-1There is characteristic peak at the place, with bibliographical information (Melissa, S. S.; Eric, R. S.; Eric, V. P.; Freeman, R. G. Inorg. Chem. 2001,40,2298) be consistent.
The cationic moiety [(ArNCH of title complex
2CH
2NAr) CH]
+Characterize by mass spectrum, find that it has a molecular ion peak at 367.2386 places, this molecular ion peak is 367.24 in theory, and actual measurement meets substantially with theory.
Proof gained compound is target compound.
Embodiment four: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=5-C (CH
3)
3-2-(OH)-C
6H
3, X's=Br) is synthetic.
Successively with [(ArNCH
2CH
2NAr) CH] the Cl(0.40 gram, 1.0 mmoles) and the NaBr(0.32 gram, 3.0 mmoles) (0.29 restrains to join ferric bromide, 1.0 in tetrahydrofuran solution mmole), 60 ℃ of lower reactions 12 hours, vacuum is taken out desolventizing, the hexane washing, drain, with the tetrahydrofuran (THF) extraction, centrifugal clear liquid shifts, and adds the hexane recrystallization in clear liquid, separate out the reddish-brown crystal under the room temperature, productive rate 78%.
Product is carried out ultimate analysis, the test fusing point, the result is as follows:
Ultimate analysis and fusing point
| ? | C：（%） | H：（%） | N：（%） |
| Theoretical value | 37.18 | 4.21 | 3.77 |
| Actual value | 37.44 | 4.51 | 3.54 |
Because the title complex of iron has paramagnetism, characterize so it is not carried out nuclear-magnetism.
This title complex [(ArNCH
2CH
2NAr) CH] FeBr
4That form with ion pair exists, [FeBr wherein
4]
-Characterize by Raman spectrum, find that it is at 204 cm
-1There is characteristic peak at the place, and (Melissa S. S, Eric R. S, Eric V. P, Freeman R. G. Inorg. Chem. 2001,40,2298) is consistent with bibliographical information.
The cationic moiety [(ArNCH of title complex
2CH
2NAr) CH]
+Characterize by mass spectrum, find that it has a molecular ion peak at 367.2403 places, this molecular ion peak is 367.24 in theory, and actual measurement meets substantially with theory.
Proof gained compound is target compound.
Embodiment five: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=2-(OH)-C
6H
4, synthetic (part synthetic referring to Charles, R. of X=Cl); Lydia, B.; Stephane, B. L.; Samuel, D. Organometallics, 2010,29,1191).
With [(ArNCH
2CH
2NAr) CH] the Cl(0.29 gram, 1.0 mmole) join in the tetrahydrofuran solution of iron trichloride (0.16 gram, 1.0 mmoles) 30 ℃ of lower reactions 2 hours, vacuum is taken out desolventizing, the hexane washing is drained, and extracts with tetrahydrofuran (THF), centrifugal clear liquid shifts, in clear liquid, add the hexane recrystallization, separate out brown crystal under the room temperature, productive rate 78%.
Product is carried out ultimate analysis, and the result is as follows:
Ultimate analysis
| ? | C：（%） | H：（%） | N：（%） |
| Theoretical value | 39.78 | 3.34 | 6.18 |
| Actual value | 40.13 | 3.52 | 6.03 |
Because the title complex of iron has paramagnetism, characterize so it is not carried out nuclear-magnetism.
This title complex [(ArNCH
2CH
2NAr) CH] FeCl
4That form with ion pair exists, [FeCl wherein
4]
-Characterize by Raman spectrum, find that it is at 332 cm
-1There is characteristic peak at the place, with bibliographical information (Melissa, S. S.; Eric, R. S.; Eric, V. P.; Freeman, R. G. Inorg. Chem. 2001,40,2298) be consistent.
The cationic moiety [(ArNCH of title complex
2CH
2NAr) CH]
+Characterize by mass spectrum, find that it has a molecular ion peak at 255.1106 places, this molecular ion peak is 255.11 in theory, and actual measurement meets substantially with theory.
Proof gained compound is target compound.
Embodiment six: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-CH
3-2-(OH)-C
6H
2, X's=Cl) is synthetic
Part synthetic referring to Charles, R.; Lydia, B.; Stephane, B. L.; Samuel, D. Organometallics, 2010,29,1191.
With [(ArNCH
2CH
2NAr) CH] the Cl(0.35 gram, 1.0 mmole) join in the tetrahydrofuran solution of iron trichloride (0.16 gram, 1.0 mmoles) 30 ℃ of lower reactions 2 hours, vacuum is taken out desolventizing, the hexane washing is drained, and extracts with tetrahydrofuran (THF), centrifugal clear liquid shifts, in clear liquid, add the hexane recrystallization, separate out brown crystal under the room temperature, productive rate 88%.
Product is carried out ultimate analysis, and the result is as follows:
Ultimate analysis
| ? | C：（%） | H：（%） | N：（%） |
| Theoretical value | 44.83 | 4.55 | 5.50 |
| Actual value | 44.90 | 4.78 | 5.28 |
Because the title complex of iron has paramagnetism, characterize so it is not carried out nuclear-magnetism.
This title complex [(ArNCH
2CH
2NAr) CH] FeCl
4That form with ion pair exists, [FeCl wherein
4]
-Characterize by Raman spectrum, find that it is at 333 cm
-1There is characteristic peak at the place, and (Melissa S. S, Eric R. S, Eric V. P, Freeman R. G. Inorg. Chem. 2001,40,2298) is consistent with bibliographical information.
The cationic moiety [(ArNCH of title complex
2CH
2NAr) CH]
+Characterize by mass spectrum, find that it has a molecular ion peak at 311.1792 places, this molecular ion peak is 311.18 in theory, and actual measurement meets substantially with theory.
Proof gained compound is target compound.
Embodiment seven: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the p-methylphenyl magnesium bromide of catalysis of X=Cl) and the linked reaction of bromocyclohexane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (6.75 milligrams of catalyzer; 0.010 mmole; 1 mol%), bromocyclohexane (122 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.56 milliliters of ether and p-methylphenyl magnesium bromide (0.94 milliliter, 1.28 mmole * milliliters
-1).30 ℃ of lower reactions 15 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 99% through the gas chromatographic analysis product yield, catalytic efficiency is 68.90g/mmol/h.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.27 (m, 1H), 1.38 (m, 4H), (1.73 m, 1H), 1.84 (m, 4H), 2.30 (s, 3H), (2.45 m, 1H), 7.08 (s, br, 4H)).
Embodiment eight: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the p-methylphenyl magnesium bromide of catalysis of X=Br) and the linked reaction of bromocyclohexane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (8.55 milligrams of catalyzer; 0.010 mmole; 1 mol%), bromocyclohexane (122 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.56 milliliters of ether and p-methylphenyl magnesium bromide (0.94 milliliter, 1.28 mmole * milliliters
-1).30 ℃ of lower reactions 15 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 97% through the gas chromatographic analysis product yield; Catalytic efficiency is 67.51 g/mmol/h.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.27 (m, 1H), 1.38 (m, 4H), (1.73 m, 1H), 1.84 (m, 4H), 2.30 (s, 3H), (2.45 m, 1H), 7.08 (s, br, 4H)).
Embodiment nine: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=5-C (CH
3)
3-2-(OH)-C
6H
3, the p-methylphenyl magnesium bromide of catalysis of X=Cl) and the linked reaction of bromocyclohexane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (6.18 milligrams of catalyzer; 0.010 mmole; 1 mol%), bromocyclohexane (122 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.56 milliliters of ether and p-methylphenyl magnesium bromide (0.94 milliliter, 1.28 mmole * milliliters
-1).30 ℃ of lower reactions 15 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 96% through the gas chromatographic analysis product yield, catalytic efficiency is 66.81 g/mmol/h.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.27 (m, 1H), 1.38 (m, 4H), (1.73 m, 1H), 1.84 (m, 4H), 2.30 (s, 3H), (2.45 m, 1H), 7.08 (s, br, 4H)).
Embodiment ten: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the p-methylphenyl magnesium bromide of catalysis of X=Cl) and the linked reaction of chlorocyclohexane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (33.75 milligrams of catalyzer; 0.050 mmole; 5 mol%), chlorocyclohexane (119 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.33 milliliters of ether and p-methylphenyl magnesium bromide (1.17 milliliters, 1.28 mmole * milliliters
-1).25 ℃ of lower reactions 40 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 92% through the gas chromatographic analysis product yield.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.27 (m, 1H), 1.38 (m, 4H), (1.73 m, 1H), 1.84 (m, 4H), 2.30 (s, 3H), (2.45 m, 1H), 7.08 (s, br, 4H)).
Embodiment 11:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the linked reaction of the catalysis p-methylphenyl magnesium chloride of X=Cl) and chlorocyclohexane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (33.75 milligrams of catalyzer; 0.050 mmole; 5 mol%), chlorocyclohexane (119 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.33 milliliters of ether and p-methylphenyl magnesium chloride (1.17 milliliters, 1.28 mmole * milliliters
-1).25 ℃ of lower reactions 40 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 85% through the gas chromatographic analysis product yield.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.27 (m, 1H), 1.38 (m, 4H), (1.73 m, 1H), 1.84 (m, 4H), 2.30 (s, 3H), (2.45 m, 1H), 7.08 (s, br, 4H)).
Embodiment 12:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the linked reaction of the catalysis o-methyl-phenyl-magnesium bromide of X=Cl) and chlorocyclohexane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (33.75 milligrams of catalyzer; 0.050 mmole; 5 mol%), chlorocyclohexane (119 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.33 milliliters of ether and o-methyl-phenyl-magnesium bromide (1.17 milliliters, 1.28 mmole * milliliters
-1).25 ℃ of lower reactions 40 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 82% through the gas chromatographic analysis product yield.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.29 (m, 1H), 1.41 (m, 4H), (1.76 m, 1H), 1.83 (m, 4H), 2.33 (s, 3H), 2.70 (m, 1H), 7.14 (m, 4H)).
Embodiment 13: [(ArNCH
2CH
2NAr) CH] FeX
4(Ar=5-C (CH
3)
3-2-(OH)-C
6H
3, the linked reaction of the catalysis o-methyl-phenyl-magnesium bromide of X=Cl) and chlorocyclohexane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (30.90 milligrams of catalyzer; 0.050 mmole; 5 mol%), chlorocyclohexane (119 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.33 milliliters of ether and o-methyl-phenyl-magnesium bromide (1.17 milliliters, 1.28 mmole * milliliters
-1).25 ℃ of lower reactions 40 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 78% through the gas chromatographic analysis product yield.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.29 (m, 1H), 1.41 (m, 4H), (1.76 m, 1H), 1.83 (m, 4H), 2.33 (s, 3H), 2.70 (m, 1H), 7.14 (m, 4H)).
Embodiment 14:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the p-methylphenyl magnesium bromide of catalysis of X=Cl) and the linked reaction of bromo heptane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (6.75 milligrams of catalyzer; 0.010 mmole; 1 mol%), bromo heptane (157 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.56 milliliters of ether and p-methylphenyl magnesium bromide (0.94 milliliter, 1.28 mmole * milliliters
-1).30 ℃ of lower reactions 15 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 90% through the gas chromatographic analysis product yield; Catalytic efficiency is 66.88 g/mmol/h.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 0.88 (t, 3H), 1.28 (m, 8H), 1.58 (m, 2H), 2.31 (s, 3H), (2.56 t, 2H), 7.07 (m, 4H)).
Embodiment 15:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the p-methylphenyl magnesium bromide of catalysis of X=Cl) and the linked reaction of chloro normal heptane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (33.75 milligrams of catalyzer; 0.050 mmole; 5 mol%), chloro normal heptane (155 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.56 milliliters of ether and p-methylphenyl magnesium bromide (1.17 milliliters, 1.28 mmole * milliliters
-1).25 ℃ of lower reactions 40 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 70% through the gas chromatographic analysis product yield.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 0.88 (t, 3H), 1.28 (m, 8H), 1.58 (m, 2H), 2.31 (s, 3H), (2.56 t, 2H), 7.07 (m, 4H)).
Embodiment 16:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the p-methylphenyl magnesium bromide of catalysis of X=Cl) and the linked reaction of chlorocyclopentane.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (33.75 milligrams of catalyzer; 0.050 mmole; 5 mol%), chlorocyclopentane (103 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.33 milliliters of ether and p-methylphenyl magnesium bromide (1.17 milliliters, 1.28 mmole * milliliters
-1).25 ℃ of lower reactions 40 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 75% through the gas chromatographic analysis product yield.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 1.57 (m, 2H), 1.68 (m, 2H), (1.77 m, 2H), 2.04 (m, 2H), 2.31 (s, 3H), (2.95 m, 1H), 7.09 (d, 2H), 7.14 (d, 2H)).
Embodiment 17:
[(ArNCH
2CH
2NAr) CH] FeX
4(Ar=3,5-di-C (CH
3)
3-2-(OH)-C
6H
2, the p-methylphenyl magnesium bromide of catalysis of X=Cl) and the linked reaction of Sec-Butyl Chloride.
In the reaction flask of processing through dehydration and deoxidation; under argon shield, add successively (33.75 milligrams of catalyzer; 0.050 mmole; 5 mol%), Sec-Butyl Chloride (106 microlitres, 1.0 mmoles); n-hexadecane (standard specimen) (29.40 microlitres; 0.10 mmole), and 1.33 milliliters of ether and p-methylphenyl magnesium bromide (1.17 milliliters, 1.28 mmole * milliliters
-1).25 ℃ of lower reactions 40 minutes, with the aqueous solution termination reaction of saturated ammonium chloride, behind the ethyl acetate extraction, be 70% through the gas chromatographic analysis product yield.
Coupled product is dissolved in CDCl
3In (approximately 0.4 mL), tube sealing measure to characterize on Unity Inova-400 type NMR instrument under the room temperature: (δ 0.82 (t, 3H), 1.21 (d, 3H), (1.56 m, 2H), 2.31 (s, 3H), 2.56 (m, 1H), 7.07 (d, 2H), 7.11 (d, 2H)).
Claims (9)
1. ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt, the iron of described ionic (III) title complex is expressed by the following chemical structure formula:
In the formula, R
1And R
2Be selected from respectively a kind of in hydrogen atom, methyl, the tertiary butyl, X is a kind of in the chlorine or bromine.
2. described ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt of claim 1 carries out the application of cross-coupling reaction as single-component catalyst catalysis aryl grignard reagent and the halogenated alkyl hydrocarbon that contains b-H.
3. application according to claim 2 is characterized in that: described halogenated alkyl hydrocarbon is the alkyl hydrochloric ether.
4. described ionic iron (III) title complex that contains bisphenol functionalized imidazoline salt of claim 1 carries out the method for cross-coupling reaction as single component catalyst catalysis aryl grignard reagent and the halogenated alkyl hydrocarbon that contains b-H, may further comprise the steps:
[1] under the anhydrous and oxygen-free condition, in inert atmosphere, adds successively the diethyl ether solution of catalyzer, halogenated alkyl hydrocarbon, solvent ether, aryl grignard reagent;
[2] 0～45 ℃ of stirring reaction 10～60 minutes, with the aqueous solution termination reaction of saturated ammonium chloride;
[3] reaction product ethyl acetate extraction, separating-purifying.
5. method according to claim 4, it is characterized in that: described inert atmosphere is nitrogen or argon gas atmosphere.
6. method according to claim 4, it is characterized in that: described halogenated alkyl hydrocarbon is the alkyl hydrobromic ether, in amount of substance, the aryl grignard reagent consumption is 1.2 times of halohydrocarbon, and catalyst levels is 1 mol% of halohydrocarbon, in the step [2], stirring reaction 15 minutes, temperature are 30 ℃.
7. method according to claim 4, it is characterized in that: described halogenated alkyl hydrocarbon is the alkyl hydrochloric ether, in amount of substance, the aryl grignard reagent consumption is 1.5 times of halohydrocarbon, and catalyst levels is 5 mol% of halohydrocarbon, in the step [2], stirring reaction 40 minutes, temperature are 25 ℃.
8. method according to claim 4, it is characterized in that: product is purified by column chromatography for separation.
9. method according to claim 4 is characterized in that: in the step [1], after adding the halogenated alkyl hydrocarbon, add n-hexadecane again, in the step [3], behind the ethyl acetate extraction, do interior mark with n-hexadecane, by the yield of gas Chromatographic Determination product.
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| CN103992231A (en) * | 2014-05-15 | 2014-08-20 | 苏州大学 | Method for synthesizing triarylated amine |
| CN106000465A (en) * | 2015-07-27 | 2016-10-12 | 苏州大学 | Method for oxidative coupling reaction of aldehyde and secondary amide |
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