CN107056599A - A kind of preparation method of beta-diketon class titanium complex - Google Patents
A kind of preparation method of beta-diketon class titanium complex Download PDFInfo
- Publication number
- CN107056599A CN107056599A CN201710441898.XA CN201710441898A CN107056599A CN 107056599 A CN107056599 A CN 107056599A CN 201710441898 A CN201710441898 A CN 201710441898A CN 107056599 A CN107056599 A CN 107056599A
- Authority
- CN
- China
- Prior art keywords
- beta
- diketon
- dichloromethane
- titanium
- titanium tetrachloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/77—Preparation of chelates of aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a kind of preparation method of beta-diketon class titanium complex, belong to organic synthesis field.Comprise the following steps：(1) titanium tetrachloride and dichloromethane are hybridly prepared into the dichloromethane solution of titanium tetrachloride；(2) beta-diketon and dichloromethane are hybridly prepared into the dichloromethane solution of beta-diketon class；(3) the beta-diketon class dichloromethane solution in the dichloromethane solution of the titanium tetrachloride in step (1) and step (2) is carried out reacting to obtain beta-diketon class titanium complex.The environmental protection of this method operating condition is gentle, and technological operation is easy, and suitable batch prepares such complex.
Description
Technical field：
The invention belongs to organic synthesis field, and in particular to be beta-diketon class titanium complex preparation method.
Background technology
Beta-diketon class titanium complex is the important catalyst for polymerization of a class, and it has stronger catalytic activity, with wide
Wealthy application prospect.The synthetic method of this kind of compound has been reported (Fay R C, Lowry R N.Stereochemistry
and lability of dihalobis(β-diketonato)titanium(IV)
complexes.I.Acetylacetonates[J].Inorg Chem,1967,6(8):1512-1519), but due to tetrachloro
Change titanium and do not do stable stateization protection so that reaction condition and operation require very harsh, and operation difficulty is big, and use solvent benzol toxicity
It is relatively strong, it is unfavorable for environmental protection and safety operation.
The content of the invention
The technical problem to be solved in the present invention is：Based on above mentioned problem, the present invention provides a kind of beta-diketon class titanium complex
The improvement of preparation method.Reaction condition of the present invention and simple to operate is nontoxic.
The present invention solves a technical scheme being used of its technical problem：It is prepared by a kind of beta-diketon class titanium complex
The improvement of method, comprises the following steps：
(1) titanium tetrachloride and dichloromethane are hybridly prepared into the dichloromethane solution of titanium tetrachloride；
(2) beta-diketon and dichloromethane are hybridly prepared into the dichloromethane solution of beta-diketon class；Described beta-diketon
For acetylacetone,2,4-pentanedione or benzoyl acetone or dibenzoyl methane
(3) by the beta-diketon class dichloromethane in the dichloromethane solution of the titanium tetrachloride in step (1) and step (2)
Solution carries out reacting to obtain beta-diketon class titanium complex.
Further, the proportioning of titanium tetrachloride and dichloromethane is 10g titanium tetrachlorides in step (1)：50ml~100ml bis-
Chloromethanes.The mass ratio of dichloromethane and titanium tetrachloride is in 6.6-13.25.
Further, reaction is specially in step (2)：Under nitrogen protection, the two of acetylacetone,2,4-pentanedione is first put into reaction vessel
Titanium tetrachloride dichloromethane solution is slowly added dropwise under chloromethanes solution, stirring, ice-water bath, room temperature reaction is stayed overnight, filtering, concentration knot
Crystalline substance, is filtered out, and is dried in vacuo to obtain beta-diketon class transient metal complex product.
Described titanium tetrachloride solution and the mol ratio of beta-diketon are 1:1-1：5.Such as, titanium tetrachloride solution and acetyl
The mol ratio of acetone is 1:2.
Beneficial effect is：It is raw material by the solution that titanium tetrachloride is configured to dichloromethane, is added into beta-diketon class
In the dichloromethane solvent of compound, dehydrochlorination beta diketone titanium complex.The environmental protection of this method operating condition is gentle, technique behaviour
Make easy, suitable batch prepares such complex.Wherein β-diacetyl acetone titanium complex elementary analysis result is as shown in table 1.
The elementary analysis result of table 1
Brief description of the drawings
Fig. 1 is β-diacetyl acetone titanium hydrogen spectrogram
Embodiment
Presently in connection with specific embodiment, the invention will be further described, following examples be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
Step 1：Titanium tetrachloride solution is configured
10g titanium tetrachlorides are added to wiring solution-forming A in 50ml dichloromethane.
Step 2：It is prepared by β-diacetyl acetone titanium
10.6g acetylacetone,2,4-pentanediones are added to wiring solution-forming B in 50ml dichloromethane.
Solution B is added in reaction bulb, then solution A is slowly dropped in B, ice-water bath temperature control, stirring is added dropwise two hours
Complete.It is stirred at room temperature 24 hours, obtains clarification red solution.Filtering, filtrate is concentrated in 30ml, refrigerator and cooled down 12 hours, analysis
Go out a large amount of Orange red solids, filter out, be dried in vacuo, obtain orange red tiny chip solid 12.9g, conversion ratio 77%.Elementary analysis
As a result：Measured value % (calculated value %) C:37.75(37.89),H:4.46(4.45).1H-NMR (CDCl3,20 DEG C, δ ppm):
5.96-6.00 (s, 2H, C=CH*-C), 2.05-2.10 (s, 12H, CH3*-C).As shown in Figure 1:7.257×10-6Place is deuterium
For chloroform solvent peak；5.972×10-6Place is the proton peak of methylene hydrogen on acetylacetone,2,4-pentanedione conjugate ring, is unimodal, peak area is
1.00；2.156×10-6Place is the proton peak of methyl hydrogen, is unimodal, peak area is 5.76；Both displacement, peak shape and peak area ratios
Example (theoretical value 1:6) architectural feature of titanium acetylacetone is met, it was demonstrated that the catalyst is successfully synthesized.
Embodiment 2
Step 1：With example one
Step 2：It is prepared by benzoyl acetone titanium
17.2g benzoyl acetones are added to wiring solution-forming C in 50ml dichloromethane.
Solution C is added in reaction bulb, then solution A is slowly dropped in B, ice-water bath temperature control, stirring is added dropwise two hours
Complete.It is stirred at room temperature 24 hours, obtains clarification red solution.Filtering, filtrate is concentrated in 30ml, refrigerator and cooled down 12 hours, analysis
Go out a large amount of Orange red solids, filter out, be dried in vacuo, obtain red chip solid 7.37g, yield 57%.Elementary analysis result：Actual measurement
Value % (calculated value %) C:53.98(54.45),H:4.08(4.11).
Embodiment 3
Step 1：With example one
Step 2：It is prepared by dibenzoyl methane titanium
23.8g dibenzoyl methanes are added to wiring solution-forming D in 50ml dichloromethane.
Solution D is added in reaction bulb, then solution A is slowly dropped in B, ice-water bath temperature control, stirring is added dropwise two hours
Complete.It is stirred at room temperature 24 hours, obtains clarification red solution.Filtering, filtrate is concentrated in 30ml, refrigerator and cooled down 12 hours, analysis
Go out a large amount of Orange red solids, filter out, be dried in vacuo, obtain red chip solid 14.24g, yield 65%.Elementary analysis result：It is real
Measured value % (calculated value %) C:63.67(63.97),H:3.74(3.92).
Using the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to its technical scope is determined according to right.
Claims (4)
1. a kind of preparation method of beta-diketon class titanium complex, it is characterised in that：Comprise the following steps：
(1) titanium tetrachloride and dichloromethane are hybridly prepared into the dichloromethane solution of titanium tetrachloride；
(2) beta-diketon and dichloromethane are hybridly prepared into the dichloromethane solution of beta-diketon class, described beta-diketon is second
Acyl acetone or benzoyl acetone or dibenzoyl methane；
(3) by the beta-diketon class dichloromethane solution in the dichloromethane solution of the titanium tetrachloride in step (1) and step (2)
Beta-diketon class titanium complex is reacted to obtain in progress.
2. preparation method according to claim 1, it is characterised in that：Dichloromethane and four chlorinations in described step (1)
The mass ratio of titanium is in 6.6-13.25.
3. preparation method according to claim 1, it is characterised in that：Reactions steps specially exist in described step (2)
Under nitrogen protection, the dichloromethane solution of beta-diketon class is first put into reaction vessel, is stirred, titanium tetrachloride is added under ice-water bath
Dichloromethane solution, room temperature reaction stayed overnight, and filters, and condensing crystallizing is filtered out, be dried in vacuo beta-diketon class transition metal is matched somebody with somebody
Composition powder.
4. the preparation method according to claim 1 or 3, it is characterised in that：Described titanium tetrachloride solution and beta-diketon
Mol ratio is 1:1-1：5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710441898.XA CN107056599B (en) | 2017-06-13 | 2017-06-13 | Preparation method of beta-diketone titanium complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710441898.XA CN107056599B (en) | 2017-06-13 | 2017-06-13 | Preparation method of beta-diketone titanium complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107056599A true CN107056599A (en) | 2017-08-18 |
| CN107056599B CN107056599B (en) | 2020-09-01 |
Family
ID=59595298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710441898.XA Active CN107056599B (en) | 2017-06-13 | 2017-06-13 | Preparation method of beta-diketone titanium complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107056599B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592366A (en) * | 2020-12-18 | 2021-04-02 | 西安凯立新材料股份有限公司 | Preparation method of titanium oxide acetylacetonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158859A (en) * | 1996-03-07 | 1997-09-10 | 中国科学院化学研究所 | Catalyst system for synthesizing syndiotactic polystyrene and its preparation |
| CN1295088A (en) * | 1999-11-04 | 2001-05-16 | 中国石油化工集团公司 | Syndiotactic polystyrene catalyst and its preparation and application |
| CN1459462A (en) * | 2002-05-24 | 2003-12-03 | 中国科学院化学研究所 | Technical method of preparing polynorbornene using beta diketone titanium non cyclopentadienyl catalyst |
-
2017
- 2017-06-13 CN CN201710441898.XA patent/CN107056599B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158859A (en) * | 1996-03-07 | 1997-09-10 | 中国科学院化学研究所 | Catalyst system for synthesizing syndiotactic polystyrene and its preparation |
| CN1295088A (en) * | 1999-11-04 | 2001-05-16 | 中国石油化工集团公司 | Syndiotactic polystyrene catalyst and its preparation and application |
| CN1459462A (en) * | 2002-05-24 | 2003-12-03 | 中国科学院化学研究所 | Technical method of preparing polynorbornene using beta diketone titanium non cyclopentadienyl catalyst |
Non-Patent Citations (2)
| Title |
|---|
| FAY R C,LOWRY R N: "Stereochemistry and lability of dihalobis(β-diketonato)titanium(IV)complexes.I. Acetylacetonates", 《INORG CHEM》 * |
| SERPONE N,FAY R C.: "Stereochemistry and lability of dihalobis(beta-diketonato)titanium(IV)complexes.II. Benzoylacetonates and dibenzoylmethanates", 《INORG CHEM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592366A (en) * | 2020-12-18 | 2021-04-02 | 西安凯立新材料股份有限公司 | Preparation method of titanium oxide acetylacetonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107056599B (en) | 2020-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108047107A (en) | The preparation method of diphenyl disenenide ether compound | |
| EP1414833B1 (en) | Novel transition-metal complexes and use thereof in transition-metal catalysed reactions | |
| Erker et al. | Nine-membered metallacyclic metaloxycarbene complexes by means of sequential coupling of butadiene with a ketone and a metal carbonyl at bis (cyclopentadienyl) zirconium | |
| CN111468191A (en) | Synthetic method of ruthenium carbene catalyst | |
| CN107056599A (en) | A kind of preparation method of beta-diketon class titanium complex | |
| CN108017618B (en) | Novel compound pyrazole aldehyde pyridine amine Schiff base and preparation method and application thereof | |
| CN102702121A (en) | New compound m-hydroxyphenyl tetrazine dicarbonamide, preparation and application thereof | |
| CN112375105B (en) | Application of N, N-coordinated divalent nickel complex containing meta-carborane ligand | |
| CN105131001A (en) | Synthetic method of unsubstituted zinc phthalocyanine | |
| CN110156658A (en) | A kind of chirality (R)-triarylmethane derivatives and its synthetic method containing substituted diphenylamine base and 3- indyl skeleton | |
| CN113651827B (en) | Preparation of pyrano [2,3-b]Process for preparing indol-2-ones | |
| CN116874479A (en) | Preparation method of coumarin 6 | |
| CN112939855B (en) | Process for preparing 1, 4-dihydropyridine derivatives containing azulene ring structure | |
| AU2021107258A4 (en) | 2-methylene-1-indanone derivative and synthesis method thereof | |
| Sakurai et al. | Chemistry of organosilicon compounds: CIV. Syntheses of novel organoelement heterocycles containing titanium and silicon | |
| CN111253334A (en) | Mild photocatalytic synthesis method of C2 ether substituted 2H-benzothiazole derivative | |
| CN112174972B (en) | Azacaroline compounds and process for their preparation | |
| CN111892486B (en) | Hydroxyl-substituted benzophenone compound and preparation method and application thereof | |
| CN116283823B (en) | Synthesis method and application of dehydroabietyl B-cyclobenzothiazole-aniline and diphenylamine compound | |
| CN112876515B (en) | Triptycene carbene allyl palladium compound and application thereof | |
| CN111909080B (en) | Preparation method of 2,3, 5-trichloropyridine | |
| CN102702120A (en) | New compound o-hydroxyphenyl tetrazine dicarbonamide, preparation and application thereof | |
| CN105131002A (en) | Synthetic method of unsubstituted cobalt phthalocyanine | |
| CN117229222A (en) | Method for synthesizing quinazoline by dehydrogenation of tetrahydroquinazoline | |
| Padolik et al. | The reactions of rhenium isocyanide complexes with acetonitrile. Formation of carbon—carbon and carbon—nitrogen bonds en route to rhenium containing heterocycles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |