CN103012489B - 2-2-acetylpyridine benzoyl hydrazine molybdenum complex and preparation method thereof - Google Patents
2-2-acetylpyridine benzoyl hydrazine molybdenum complex and preparation method thereof Download PDFInfo
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- CN103012489B CN103012489B CN201110369948.0A CN201110369948A CN103012489B CN 103012489 B CN103012489 B CN 103012489B CN 201110369948 A CN201110369948 A CN 201110369948A CN 103012489 B CN103012489 B CN 103012489B
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- acetylpyridine
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Abstract
The present invention relates to a kind of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex and preparation method thereof, mainly solve the problem of previous patent all unexposed molybdenum Schiff coordination compound.The present invention has following chemical structural formula by adopting:
wherein, R
1be selected from-OHR
2or
r
2for C
nh
2n+1, the technical scheme of n=2 ~ 10 solves this problem preferably, can be used in the industrial production of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex.
Description
Technical field
The present invention relates to a kind of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex and preparation method thereof.
Background technology
Schiff refers to the class organic compound containing imines or azomethine characteristic group (-RC=N-), and it is generated by the carbonyl of aldehyde ketone and amino condensation under certain conditions.Due to the hyperconjugation of C=N key and phenyl ring, this compounds is general all more stable.Phenyl ring contains the Schiff of the co-ordinating functionality such as-OH and-N, and intramolecular hydrogen bond effect makes it have rigid structure, very easily forms complex compound as polydentate ligand and high-valency metal.Therefore, Schiff occupies critical role in coordination chemistry.
Schiff is the important organic synthesis reagent of a class and intermediate.Schiff compounds and metal complexes thereof have important application at catalytic field, be widely used in the oxidation of phenols, organic intermediate is produced in the oxidation etc. of sulfide, especially some expensive organic intermediates,, they are used to agricultural chemicals, chiral drug, rubber accelerator, epoxy resin, dyestuff etc.Document CN1651472A discloses a kind of Schiff IVB race title complex containing olefin oxy, and the product of the salicylic aldehyde condensation p-aminophenyl alkylene ether that it replaces with alkyl, for part, with titanium or zirconium for active centre, prepares the catalyzer for vinyl polymerization.Document CN1814645A discloses a kind of Schiff Al catalysts preparation method for rac-Lactide ring-opening polymerization, it is characterized in that reacting the product and derivative thereof that generate for catalyzer, for rac-Lactide ring-opening polymerization with beta-diketon class Schiff and aluminium triethyl.Document CN101108367A discloses a kind of catalyzer for the synthesis of phenyl aldehyde and preparation method, it is characterized in that taking chromium as active centre, O-Phenylene Diamine salicylaldehyde is part, obtained chromium Schiff base complex, be carrier again with silica gel, as catalyst benzyl alcohol oxidation synthesizing benzaldehyde.Document CN101020747A discloses a kind of catalyzer for the synthesis of polycarbonate, it with containing the salicylic aldehyde condensation diamines of quaternary ammonium salt or quaternary alkylphosphonium salt group or three aminated compounds products for part, cobalt, chromium or aluminium are active centre.But up to now, have no the report of molybdenum Schiff complex compound.
Summary of the invention
One of technical problem to be solved by this invention is the problem of previous patent all unexposed molybdenum Schiff complex compound, provides a kind of new 2-2-acetylpyridine benzoyl hydrazine molybdenum complex.Two of technical problem to be solved by this invention is to provide a kind of preparation method of the 2-2-acetylpyridine benzoyl hydrazine molybdenum complex corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex, has following chemical structural formula:
Wherein, R
1be selected from-OHR
2or
r
2for C
nh
2n+1, n=2 ~ 10.
In technique scheme, R
1be selected from-OHC
2h
5or
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex, comprise the following steps: 2-acetopyridine and benzoyl hydrazine leave standstill after reacting 10 ~ 360 minutes in 10 ~ 100 DEG C in a solvent, after 1 ~ 7 day, precipitate is through being separated drying, obtains 2-acetylpyridine contracting benzoyl hydrazine Schiff complex compound; 2-acetylpyridine contracting benzoyl hydrazine Schiff complex compound is stirred in 10 ~ 100 DEG C in a solvent and dissolves completely, add molybdenum presoma, continue reaction 30 ~ 360 minutes, precipitate, through being separated drying, obtains described 2-2-acetylpyridine benzoyl hydrazine molybdenum complex; Wherein, the mol ratio of benzoyl hydrazine, solvent, 2-acetopyridine and molybdenum presoma is 1: (8.6 ~ 800): (0.25 ~ 4): (0.1 ~ 10).
In technique scheme, described molybdenum presoma is selected from acetyl acetone; Described solvent is selected from
or C
nh
2n+1oH, wherein n=2 ~ 10; Preferred version is for being selected from C
2h
5oH.
2-2-acetylpyridine benzoyl hydrazine molybdenum complex preparation method technique of the present invention is simple; Reaction conditions is gentle, simple to operate, safety; With acetyl acetone MoO
2(acac)
2as the molybdenum presoma of cheapness, cost is low, and environmental protection, environmentally friendly; The 2-2-acetylpyridine benzoyl hydrazine molybdenum complex stability of preparation is better; Excellent catalytic performance is shown to the epoxidation of alkene.2-2-acetylpyridine benzoyl hydrazine molybdenum complex of the present invention is used for the epoxidation reaction of tertbutyl peroxide and propylene; 100 DEG C, 3.2MPa, tertbutyl peroxide and propylene mol ratio be 1: under (2 ~ 3) condition; tertbutyl peroxide transformation efficiency can reach 46.3%; the selectivity of propylene oxide can reach 95%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrum of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex of the present invention.
In Fig. 1, concrete IR absorption band is allocated as follows:
Note: Vs is symmetrical stretching vibration, and Vas is asymmetric stretching vibration.
Embodiment
[embodiment 1]
Take 10 mmole benzoyl hydrazines, put into the round-bottomed flask (50 milliliters) containing 20 milliliters of dehydrated alcohols, 50 DEG C of heated and stirred, add 10 mmole 2-acetopyridine after benzoyl hydrazine dissolves completely, stir after 1 hour and leave standstill, after 7 days, adularescent needle crystal is separated out.Suction filtration, namely a small amount of washing with alcohol obtains 2-acetylpyridine contracting benzoyl hydrazine Schiff complex compound.
Take 5mmol2-acetylpyridine contracting benzoyl hydrazine Schiff complex compound; put into the round-bottomed flask (50ml) containing 15ml dehydrated alcohol; 75 DEG C of heated and stirred; 5mmol acetyl acetone is added after 2-acetylpyridine contracting benzoyl hydrazine dissolves completely; have orange powder to separate out, continuation heated and stirred suction filtration after 2 hours, washing with alcohol final vacuum 40 DEG C is dry obtains orange powder product; its structural formula is as follows, and its infrared analysis spectrum is shown in Fig. 1.
[embodiment 2]
Take 10 mmole benzoyl hydrazines, put into the round-bottomed flask (50 milliliters) containing 20 milliliters of pyridines, 50 DEG C of heated and stirred, add 10 mmole 2-acetopyridine after benzoyl hydrazine dissolves completely, stir after 1 hour and leave standstill, after 7 days, adularescent needle crystal is separated out.Suction filtration, namely a small amount of washing with alcohol obtains 2-acetylpyridine contracting benzoyl hydrazine Schiff complex compound.
Take 5mmol2-acetylpyridine contracting benzoyl hydrazine Schiff complex compound; put into the round-bottomed flask (50ml) containing 15ml pyridine; 75 DEG C of heated and stirred; 5mmol acetyl acetone is added after 2-acetylpyridine contracting benzoyl hydrazine dissolves completely; have orange powder to separate out, continuation heated and stirred suction filtration after 2 hours, pyridine washing final vacuum 40 DEG C is dry obtains product; its structural formula is as follows, and its infrared analysis spectrum is similar to Fig. 1.
[embodiment 3]
Get tertbutyl peroxide, 2-2-acetylpyridine benzoyl hydrazine molybdenum complex that n-propyl alcohol and [embodiment 1] are synthesized puts into autoclave, after sealed reactor, start heated and stirred.When reaching default 100 DEG C, high-pressure pump pumps into propylene, and propylene amount is determined by pumping into volume.Reaction timing, arrives and takes off reactor after 2 hours, be cooled to 10 ~ 15 DEG C with frozen water, gets liquid phase in freezing sampler.Sampler is continued to outward winding after freezing 30 minutes purging valve at subzero 20 DEG C, opens sampler after slowly being released by the propylene in sampler, seal after fast remaining liq being transferred to chromatography column feed materials bottle, carry out stratographic analysis.
Reaction conditions: temperature of reaction 100 DEG C, 2 hours reaction times, rotating speed 540rpm, tertbutyl peroxide (TBHP) add-on 70 mmole, n-propyl alcohol add-on 50 mmole, catalyst charge 0.1 mmole, 60 milliliters of reactors, passing into propylene to pressure is 3.2MPa.
Reaction result: tertbutyl peroxide transformation efficiency can reach 46.3%, the selectivity of propylene oxide can reach 95%.
Claims (5)
1. a 2-2-acetylpyridine benzoyl hydrazine molybdenum complex, has following chemical structural formula:
Wherein, R
1be selected from-OHR
2or
r
2for C
nh
2n+1, n=2 ~ 10.
2. 2-2-acetylpyridine benzoyl hydrazine molybdenum complex according to claim 1, is characterized in that R
1be selected from-OHC
2h
5or
3. the preparation method of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex described in claim 1, comprise the following steps: 2-acetopyridine and benzoyl hydrazine leave standstill after reacting 10 ~ 360 minutes in 10 ~ 100 DEG C in a solvent, after 1 ~ 7 day, precipitate is through being separated drying, obtains 2-acetylpyridine contracting benzoyl hydrazine Schiff; 2-acetylpyridine contracting benzoyl hydrazine Schiff be stirred in 10 ~ 100 DEG C in a solvent and dissolve completely, add molybdenum presoma, continue reaction 30 ~ 360 minutes, precipitate, through being separated drying, obtains described 2-2-acetylpyridine benzoyl hydrazine molybdenum complex; Wherein, the mol ratio of benzoyl hydrazine, solvent, 2-acetopyridine and molybdenum presoma is 1:(8.6 ~ 800): (0.25 ~ 4): (0.1 ~ 10); Described molybdenum presoma is selected from acetyl acetone.
4. the preparation method of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex according to claim 3, is characterized in that described solvent is selected from
or C
nh
2n+1oH, wherein n=2 ~ 10.
5. the preparation method of 2-2-acetylpyridine benzoyl hydrazine molybdenum complex according to claim 4, is characterized in that described solvent is selected from C
2h
5oH.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001017530A1 (en) * | 1999-09-02 | 2001-03-15 | University Of Queensland | Iron chelators and uses thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001017530A1 (en) * | 1999-09-02 | 2001-03-15 | University Of Queensland | Iron chelators and uses thereof |
Non-Patent Citations (4)
| Title |
|---|
| New Chloro, μ-Oxo, and Alkyl Derivatives of Dioxomolybdenum(VI) and -Tungsten(VI) Complexes Chelated with N2O Tridentate Ligands:Synthesis and Catalytic Activities toward Olefin Epoxidation;Yee-Lok Wong等，;《Inorg. Chem.》;20021209;第41卷(第20期);第5276-5285页 * |
| Synthesis, characterization and antifungal studies of oxomolybdenum (V) complexes of Schiff bases derived from hydrazine carboxamide and thiosemicarbazide;RAHUL KUMAR RASTOGI等，;《Oriental Journal of Chemistry》;20081231;第24卷(第3期);第1043-1048页 * |
| 异烟酰肼缩水杨醛Schiff碱配合物的合成与表征;解庆范等，;《化学研究》;20080331;第19卷(第1期);第39-42页 * |
| 稀土-异烟酰肼席夫碱配合物的设计合成与结构;李庚等，;《无机化学学报》;20081130;第24卷(第11期);第1767-1771页 * |
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