CN105669431A - Three-dimensional manganese formate dehydrate complex single crystal and application - Google Patents
Three-dimensional manganese formate dehydrate complex single crystal and application Download PDFInfo
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- CN105669431A CN105669431A CN201610255080.4A CN201610255080A CN105669431A CN 105669431 A CN105669431 A CN 105669431A CN 201610255080 A CN201610255080 A CN 201610255080A CN 105669431 A CN105669431 A CN 105669431A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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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
- B01J31/22—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
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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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
- 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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- 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
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Abstract
The invention discloses a three-dimensional manganese formate dehydrate complex single crystal, as well as a preparation method and an application thereof. The structure of the complex single crystal is [Mn (COO) 3].2H2O. Meanwhile, the invention also discloses the preparation method of the single crystal. A room-temperature volatilization method is adopted, that is, MnC12.4H2O and formic acid are stirred in water for half an hour, and then filtered, and after filtrate is volatilized for two weeks, a colorless bulk crystal suitable for X-ray single-crystal diffraction is obtained, wherein the molar ratio of formic acid to MnC12.4H2O is 1 to 1. The invention further discloses the application of specificity of the three-dimensional manganese formate dehydrate complex single crystal as a catalyst in generation of 4, 4'-difluorobiphenyl from fluorophenylboronic acid.
Description
The present invention obtains the subsidy of Tianjin Education Commission innovation team (TD12-5037).
Technical field
The invention belongs to organic and Inorganic synthese technical field, it relates to three vitamin A acid manganese complex monocrystalline [Mn (COO)3]·2H2The preparation method of O and the application as catalyzer aspect.
Background technology
Formic acid and derivative thereof are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound. These parts can form chelating or bridging pattern with multiple bridging mode and metallic ion coordination. Special purpose for formic acid compound also shows in the design of molecular device, and the metal complexes that synthesis has a different dimension has been the most important step of device.
The present invention adopts normal temperature volatilization method, i.e. MnCl2·4H2O and formic acid filter after stirring half an hour in water, and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks, structure is [Mn (COO)3]·2H2O. This title complex also can be used as the catalyzer that fluorobenzoic boric acid generates 4,4'-DfBP and applied.
Summary of the invention
Current inventor provides following technical scheme for this reason:
The monocrystalline of a kind of three vitamin A acid manganese complexes, it is characterized in that this single crystal structure adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, obtain unit cell parameters through least-squares refinement, utilize software to solve monocrystalline data from difference fourier electron density map:
Its structure is as follows:
[Mn(COO)3]·2H2O。
The present invention further discloses the preparation method of three vitamin A acid manganese complex monocrystalline, it is characterised in that it adopts normal temperature volatilization method, by MnCl2·4H2O and formic acid filter after stirring half an hour in water, and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks; Wherein formic acid: MnCl2·4H2The mol ratio of O is 1:1;
The structure of three vitamin A acid manganese complex monocrystalline is [Mn (COO)3]·2H2O。
The present invention further discloses three vitamin A acid manganese complex monocrystalline specificities and is applied by the catalyzer that fluorobenzoic boric acid generates 4,4'-DfBP, and experimental result shows:
(1) catalyzer that fluorobenzoic boric acid generates 4,4'-DfBP is had good catalytic effect by the complex monocrystal specificity in embodiment 2, and catalysis product rate reaches 96%;
(2) 3-methoxyphenylboronic acid, 1-naphthalene phenylo boric acid, 4-methylthio phenyl boric acid, 4-chlorobenzene boric acid, 4-pyridine phenylo boric acid catalytic effect are not generally even reacted by complex monocrystal.
The advantage and disadvantage that a kind of three vitamin A acid manganese complex monocrystalline disclosed by the invention have is:
(1) operation is simple and easy to do.
(2) reaction yield height, the purity height of products obtained therefrom.
(3) three vitamin A acid manganese complex monocrystalline prepared by the present invention, production cost is low, and method is easy, is applicable to scale operation. To in fluorobenzoic boric acid generation 4,4'-DfBP, there is good catalytic effect in catalysis.
Accompanying drawing explanation
Fig. 1: the crystalline structure figure of complex monocrystal;
Fig. 2: the tomograph of complex monocrystal;
Fig. 3: 4,4'-DfBP1HNMR schemes.
Embodiment
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, never means that it limits the scope of the invention by any way. Raw materials used all have commercially available. All raw materials are all buy from domestic and international chemical reagents corporation, such as formic acid and MnCl2·4H2The raw materials such as O, it does not have through continuation purify but directly use.
Embodiment 1
Formic acid (0.1mmol) and MnCl2·4H2O (0.1mmol) filters after stirring half an hour in water (10mL), and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks. Product rate: 40%. Ultimate analysis (C18H42Mn6O48) theoretical value (%): C, 15.94; H, 3.12. Measured value: C, 15.86; H, 3.15.
Embodiment 2
Crystal structure determination adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, unit cell parameters is obtained through least-squares refinement, software is utilized to solve crystalline structure from difference fourier electron density map, and through Lorentz lorentz and polarizing effect correction. All H atom are synthesized by difference fourier and are determined through desirable position calculation. Detailed axonometry data:
Embodiment 3
Specificity is as the concrete instance of catalyzer
Method: fluorobenzoic boric acid (0.82mmol) and cesium carbonate (0.01g) are dissolved in 3mLDMF by replacement, add 5mg catalyzer, stirred at ambient temperature 5 hours, CH2Cl2Extraction, washing, dry, filter, de-molten, thick product obtains product through petrol ether/ethyl acetate mixed solution (v:v=1:1) through silica gel column chromatography wash-out.
Result: obtain 4,4'-DfBP 0.0748g, the catalysis product rate calculated is 96%.
Embodiment 5
Conclusion:
(1) three vitamin A acid manganese complex does not play any katalysis for catalytic substrate 1-naphthalene phenylo boric acid.
(2) three vitamin A acid manganese complexes are general for the catalytic effect of 3-methoxyphenylboronic acid, 4-methylthio phenyl boric acid, 4-chlorobenzene boric acid, 4-pyridine phenylo boric acid, and catalysis product rate is between 4-17%.
(3) three vitamin A acid manganese complexes are best for the catalytic effect of catalytic substrate 4-fluorobenzoic boric acid, and catalysis product rate is up to 96%.
After the better embodiment illustrated in detail, it is familiar with this skilled worker can be well understood to, do not depart from above-mentioned claim with spirit under can carry out various change and amendment, all any simple modification, equivalent variations and modifications above embodiment done according to the technical spirit of the present invention, all belong to the scope of technical solution of the present invention. And the present invention does not also implement the restriction of mode by example in specification sheets.
Claims (3)
1. the monocrystalline of a vitamin A acid manganese complex, it is characterized in that this single crystal structure adopts APEXIICCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray, λ=0.71073 is incident radiation, point diffraction is collected with ω-2 θ scan mode, obtain unit cell parameters through least-squares refinement, utilize software to solve monocrystalline data from difference fourier electron density map:
Its structure is as follows:
[Mn(COO)3]·2H2O。
2. the preparation method of three vitamin A acid manganese complex monocrystalline described in claim 1, it is characterised in that it adopts normal temperature volatilization method, i.e. MnCl2·4H2O and formic acid filter after stirring half an hour in water, and filtrate normal temperature obtains the colourless bulk crystals of applicable X-ray single crystal diffraction after volatilizing two weeks, wherein formic acid: MnCl2·4H2The mol ratio of O is 1:1;
The structure of three vitamin A acid manganese complex monocrystalline is [Mn (COO)3]·2H2O。
3. fluorobenzoic boric acid is generated the application of the catalyzer aspect of 4,4'-DfBP by three vitamin A acid manganese complex monocrystalline specificities described in claim 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497018A (en) * | 2014-12-15 | 2015-04-08 | 天津师范大学 | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex |
| CN105418657A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | 1,4-dimethyl-2,5-dimethylene bis(triazole)isophthalic acid-included dimethylacetamide cadimium complex single crystal and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497018A (en) * | 2014-12-15 | 2015-04-08 | 天津师范大学 | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex |
| CN105418657A (en) * | 2016-01-05 | 2016-03-23 | 天津师范大学 | 1,4-dimethyl-2,5-dimethylene bis(triazole)isophthalic acid-included dimethylacetamide cadimium complex single crystal and application |
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Application publication date: 20160615 |