CN104557985B - Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex - Google Patents

Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex Download PDF

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CN104557985B
CN104557985B CN201410767920.6A CN201410767920A CN104557985B CN 104557985 B CN104557985 B CN 104557985B CN 201410767920 A CN201410767920 A CN 201410767920A CN 104557985 B CN104557985 B CN 104557985B
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triazole
copper complex
oxygen ether
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triazole copper
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CN104557985A (en
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王英
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Tianjin Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Abstract

The invention discloses an oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and a preparation method of the oxygen ether dual-triazole copper complex. The complex is prepared from Cu(NO3)2 and L by adopting a 'normal temperature volatilization method' under normal temperature stirring and volatilization conditions. The invention further discloses application of (Cu(L)2(NO3)2)(1)(L=1-(4-(4-(1H-1, 2, 4-triazole-1-yl) phenoxy) phenyl)-1H-1, 2, 4-triazole) as a coupling reaction catalyst of p-fluorophenylboronic acid.

Description

Have and be catalyzed double triazole copper complex of the oxygen ether to fluorobenzoic boric acid and preparation method thereof
The present invention obtains state natural sciences fund general project (21471113), Tianjin Municipal Education Commission funded projects (20140506), Tianjin Normal University's Middl-age and youth faculty Academic innovations propulsion planning item and Tianjin innovation team of institution of higher education Training plan subsidizes (td12-5038).
Technical field
The invention belongs to Inorganic synthese technical field, it is related to copper complex [cu (l)2(no3)2] (1) (l = 1-(4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole) preparation method and as to fluorobenzene The application of the catalyst aspect of boric acid coupling reaction.
Background technology
One active field is always with the research that transition metal complex catalysis carries out high selectivity.With common Synthesizing mean is difficult to the reaction realized, and busy use transition metal complex can a step complete in a mild condition.Therefore, adopt Make catalyst of metal complex and develop the organic synthesis of high selectivity, high conversion, be very interesting Problem.In organic synthesiss, typically conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex show many Sample catalysiss.Palladium catalysed cross coupling reaction species is a lot, and these reactions are in synthesis of natural product, polymer, functional material, liquid All have been widely used in crystalline substance, drug molecule and bioactive compound.But palladium catalyst is relatively costly, if can be with cheap Copper complex replaces expensive palladium catalyst, realizes the process of reaction, not only can be cost-effective, and is expected to industrial metaplasia Produce.
1,2,4- triazole and its derivant have the coordination feature of pyrazoles and imidazoles concurrently, are that the stronger bridging of coordination ability is joined Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present.These parts can be former with the nitrogen on 1,2 Son and metallic ion coordination form n1, n2- bridging pattern, and for 4 unsubstituted 1,2,4- triazole derivatives can pass through 2,4 On nitrogen-atoms formed n2, n4- bridging pattern, this n2, n4- bridging pattern is with the n1 of imidazoles in metalloenzyme, n3- bridging pattern Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimensions Metal complex is to complete the vital step of device.
The present invention is from cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h- 1,2,4- triazole (l) prepares copper complex [cu (l) under normal temperature condition2(no3)2] (1).Catalysis experiments prove, this is joined Compound can be applied as to the catalyst of fluorobenzoic boric acid coupling reaction.
Content of the invention
Further object is that providing a kind of isophthalic double triazole copper complex [cu (l)2(no3)2] (1) monocrystalline And preparation method thereof.
For this current inventor provides following technical scheme:
The double triazole copper complex [cu (l) of oxygen ether2(no3)2] (1) (l=1- (4- (4- (1h-1,2,4- triazole -1- Base) phenoxy group) phenyl) -1h-1,2,4- triazole) structural motif as shown in Figure 1.
The present invention further discloses the double triazole copper complex [cu (l) of oxygen ether2(no3)2] (1) (l = 1-(4-(4- (1h-1,2,4- triazole -1- bases) phenoxy group) phenyl) -1h-1,2,4- triazoles) monocrystalline it is characterised in that this monocrystalline knot Structure adopt apex ii ccd single crystal diffractometer, using through graphite monochromatised mok alpha ray (λ=0.71073) be incidence Radiation, withω-2θScan mode collects point diffraction, obtains cell parameter through least square refinement, from difference Fourier electricity Sub- density map solves single crystal data using software:
The crystallographic data of table 1. coordination compound 1
The double triazole copper complex [cu (l) of oxygen ether of the present invention2(no3)2] (1) (l = 1-(4-(4-(1h-1,2,4- Triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazoles) monocrystalline preparation method, its feature is using " room temperature at it Volatility process ", i.e. cu (no3)2Get off to obtain to be suitable for the yellow rhabdolith of x- ray single crystal diffraction with l stirring at normal temperature volatilization condition. Wherein ch3Oh and h2The volume ratio of o is 4:6, cu (no3)2Mol ratio with l is 1:1；
The more detailed preparation method of the present invention is as follows:
A kind of double triazole copper complex [cu (l) of oxygen ether2(no3)2] (1) (l=1- (4- (4- (1h-1,2,4- tri- nitrogen Azoles -1- base) phenoxy group) phenyl) -1h-1,2,4- triazoles) monocrystalline preparation method, its feature it using " room temperature volatilize Method ", i.e. cu (no3)2Get off to obtain to be suitable for the yellow rhabdolith of x- ray single crystal diffraction with l stirring at normal temperature volatilization condition.Wherein ch3Oh and h2The volume ratio of o is 4:6, cu (no3)2Mol ratio with l is 1:1；
Solvent of the present invention is mixed solvent, ch3Oh and h2o.
Wherein cu (no3)2Mol ratio with l is 1:1.
The present invention further discloses a kind of double triazole copper complex of oxygen ether has catalysis to fluorobenzoic boric acid coupling reaction Effect.
A kind of double triazole copper complex [cu (l) of oxygen ether disclosed by the invention2(no3)2] (1) (l = 1-(4-(4-(1h- 1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole) monocrystalline had the advantage that to be with feature:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) [the cu (l) prepared by the present invention2(no3)2] (1) (l=1- (4- (4- (1h-1,2,4- triazole -1- Base) phenoxy group) phenyl) -1h-1,2,4- triazoles) low production cost, method simplicity, suitable large-scale production.
Brief description
The crystal structure primitive figure of Fig. 1: coordination compound 1；
The one-dimensional catenary structure figure of Fig. 2: coordination compound 1.
The nuclear-magnetism figure of Fig. 3: 4,4'- DfBP.
Specific embodiment
With reference to embodiment, the present invention is described further, and embodiment is only explanatory, is in no way intended to it Limit the scope of the present invention by any way.All of raw material is all to be bought from chemical reagents corporation both domestic and external, does not have Use through continuation purification but directly.Wherein cu (no3)2, ch3Oh is by commercially available.
Embodiment 1
The preparation of 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole (l)
1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole of the present invention Preparation method, its feature is adopting " one kettle way ", in dmf polar solvent, by 1,1,2,2- tetra- (4- bromophenyl) ethylene, three Azoles, potassium carbonate and copper oxide prepare this organic compound in a heated condition；Wherein 4,4 '-dibromodiphenyl ether: triazole: carbonic acid Potassium: the mol ratio of copper oxide is 2:10:30:1；
150 DEG C of reaction temperature, 18 hours response time.
Embodiment 2
cu(no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole L the mol ratio of () is 1:1；
L (0.0304 g, 0.1 mmol) and cu (no3)2(0.0242 g, 0.1 mmol) is in h2O (6 ml) and ch3Filter after stirring at normal temperature half an hour in the mixed solvent of oh (4 ml), filtrate room temperature volatilizees what x- ray single crystal diffraction was analyzed Yellow rhabdolith.Yield: 45% (being calculated based on l).Elementary analysiss (c32h24cun14o8) theoretical value (%): c, 48.27；H, 3.04；N, 24.63.Measured value: c, 48.25；H, 3.16；N, 24.66.
Embodiment 3
Crystal structure determination adopts apex ii ccd single crystal diffractometer, using through graphite monochromatised mok alpha ray (λ= 0.71073) it is incident radiation, withω-2θScan mode collects point diffraction, obtains structure cell ginseng through least square refinement Number, solves crystal structure from difference Fourier electron density map using software, and through Lorentz lorentz and polarity effect correction.All of H atom is synthesized and determined through preferable position calculation by difference Fourier.Detailed axonometry data is shown in Table 1.Structural motif is shown in Fig. 1, one-dimensional catenary structure is shown in Fig. 2.
The crystallographic data of table 1. coordination compound 1
Embodiment 4
cu(no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole L () mol ratio is 1:1；
We also attempted other ratios, such as cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) benzene oxygen Base) phenyl) -1h-1, the mol ratio of 2,4- triazoles (l) is 2:1, then the length of no matter the hydro-thermal reaction time, all cannot get crystalline substance State compound.Therefore cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- three The mol ratio of nitrogen azoles (l) is optimum response proportioning for 1:1.
Embodiment 5
One active field is always with the research that transition metal complex catalysis carries out high selectivity.With common Synthesizing mean is difficult to the reaction realized, and busy use transition metal complex can a step complete in a mild condition.Therefore, adopt Make catalyst of metal complex and develop the organic synthesis of high selectivity, high conversion, be very interesting Problem.In organic synthesiss, typically conventional transition metal has nickel, palladium, copper, ruthenium, rhodium, manganese etc., and wherein palladium complex show many Sample catalysiss.Palladium catalysed cross coupling reaction species is a lot, and these reactions are in synthesis of natural product, polymer, functional material, liquid All have been widely used in crystalline substance, drug molecule and bioactive compound.But palladium catalyst is relatively costly, if can be with cheap Copper complex replaces expensive palladium catalyst, realizes the process of reaction, not only can be cost-effective, and is expected to industrial metaplasia Produce.
1,2,4- triazole and its derivant have the coordination feature of pyrazoles and imidazoles concurrently, are that the stronger bridging of coordination ability is joined Body, has synthesized and has characterized substantial amounts of monokaryon, multinuclear and multidimensional compound at present.These parts can be former with the nitrogen on 1,2 Son and metallic ion coordination form n1, n2- bridging pattern, and for 4 unsubstituted 1,2,4- triazole derivatives can pass through 2,4 On nitrogen-atoms formed n2, n4- bridging pattern, this n2, n4- bridging pattern is with the n1 of imidazoles in metalloenzyme, n3- bridging pattern Similar.Specific use for triazole class compounds is also manifested by the design of molecular device, and synthesis has different dimensions Metal complex is to complete the vital step of device.
The present invention is from cu (no3)2With 1- (4- (4- (1h-1,2,4- triazole -1- base) phenoxy group) phenyl) -1h- 1,2,4- triazole (l) prepares copper complex [cu (l) in room temperature volatilization2(no3)2] (1).Catalysis experiments prove, This coordination compound can be applied as to the catalyst of fluorobenzoic boric acid coupling reaction.
Weigh 1 g to fluorobenzoic boric acid in 25 ml beakers, 0.2 g cs2co3, (the cooperation of 3 ml dmf and 0.1 g catalyst Thing 1), stir 1 hour under room temperature, tlc monitoring (pe:ea=1:1) reaction is complete, 10 ml ch2cl2Again with 20 after extracted products Ml distilled water wash, organic faciess sewage mgso4It is dried, filter, precipitation, the crude product obtaining strips post with petroleum ether, obtains To 4,4'- DfBP.

Claims (2)

1. application in terms of preparation is as the coupling reaction catalyst to fluorobenzoic boric acid for the double triazole copper complex monocrystalline of oxygen ether, its It is characterised by that this mono-crystalline structures adopts apex ii ccd single crystal diffractometer, using through graphite monochromatised mok alpha ray, λ= 0.71073 is incident radiation, withω-2θScan mode collects point diffraction, obtains structure cell ginseng through least square refinement Number, solves single crystal data from difference Fourier electron density map using software:
The molecular formula of the double triazole copper complex monocrystalline of described oxygen ether: [cu (l)2(no3)2], wherein l=1- (4- (4- (1h-1, 2,4- triazole -1- base) phenoxy group) phenyl) -1h-1,2,4- triazole.
2. application according to claim 1, wherein as follows to the method for fluorobenzoic boric acid coupling reaction:
Weigh 1 g to fluorobenzoic boric acid in 25 ml beakers, 0.2 g cs2co3, the catalyst complexes of 3 ml dmf and 0.1 g Monocrystalline, stirs 1 hour under room temperature, and tlc monitors, 10 ml ch2cl2Again with 20 ml distilled water washs, organic faciess after extracted products Use anhydrous mgso4It is dried, filter, precipitation, the crude product obtaining strips post with petroleum ether, obtains 4,4'- DfBP.
CN201410767920.6A 2014-12-15 2014-12-15 Oxygen ether dual-triazole copper complex capable of catalyzing p-fluorophenylboronic acid and preparation method of oxygen ether dual-triazole copper complex Expired - Fee Related CN104557985B (en)

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