CN105294581B - A kind of preparation method of quinocetone - Google Patents
A kind of preparation method of quinocetone Download PDFInfo
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- CN105294581B CN105294581B CN201510801547.6A CN201510801547A CN105294581B CN 105294581 B CN105294581 B CN 105294581B CN 201510801547 A CN201510801547 A CN 201510801547A CN 105294581 B CN105294581 B CN 105294581B
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- quinocetone
- magnetic
- quaternary ammonium
- ammonium salt
- solid base
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
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Abstract
The invention discloses a kind of preparation method of quinocetone, methods described is：Using benzofuraxan, acetylacetone,2,4-pentanedione and benzaldehyde as raw material, using magnetic mg_al hydrotalcite solid base and basic quaternary ammonium salt as catalyst, using absolute ethyl alcohol as solvent, reacted 1~10 hour at 10~100 DEG C, after reaction terminates, reaction solution is post-treated to obtain quinocetone；It is easily separated that the application of magnetic mg_al hydrotalcite solid base catalyst of the present invention relative to conventional technique becomes simple, easy to operate, product, and environmental pollution is small, is suitable for the industrialized production of certain scale, turns into a clean synthetic route of green.
Description
(1) technical field
The present invention relates to a kind of synthetic method of quinocetone, magnetic made from especially a kind of applied magnetic magnalium hydrotalcite
The novel environment-friendly process of solid base and basic quaternary ammonium salt composite catalyzing one pot reaction technology synthesis quinocetone.
(2) background technology
Recently as the increase and extensive approval of the whole society to sustainable stable development of environmental protection pressure, greenization
Increasingly by national governments, academia and enterprise paid attention to.Develop high selectivity, efficient catalyst, simplify reaction step
Suddenly, disposal of pollutants is reduced, develops new cleaning production technology, efficient chemical reaction is realized, realizes " zero-emission ", use solid acid
Alkali replaces liquid acid-base catalysis organic reaction to reduce pollution, increases the activity and selectivity of catalyst, while pass through recovery
Regenerate reusable, solid acid alkali catalytic is as one of main contents of Green Chemistry research.
Quinocetone is national a kind of novel chiral synthon that China initiates in the world.By suppressing the synthesis of DNA of bacteria, suppress
The growth and breeding of pathogenic microorganism in digestion, prevents or reduces disease, protects intestinal beneficial flora and intestinal wall not by micro- life
Thing or parasite infringement, promote the digestion and absorption of various nutrients, so as to accelerate growth of animal, improve food conversion ratio.Quinoline alkene
Ketone can also be used for aquaculture antibacterial growth promotion, improve survival rate, can clarify water body, improve water quality.
At present, the synthesis of quinocetone mainly has two kinds of synthetic methods.One kind is using benzofuraxan as initiation material, with benzal
Acetylacetone,2,4-pentanedione single step reaction synthesizes.The technique is shorter, the reactant mixture palpus night of aging crystallization one, as one of main reaction raw material
Benzal acetylacetone,2,4-pentanedione is difficult to purchase, and used catalyst n-butanol sodium is unstable, has corrosivity and toxicity, while price is held high
It is expensive, all need voluntarily to prepare, it is difficult to large-scale industrial production；Another kind is also using benzofuraxan as initiation material, with levulinic
Ketone and benzaldehyde react synthesis in two steps.Key reaction raw material is easy to get used in this process route, and reaction condition is gentle, suitable for industry
Metaplasia is produced, but used catalyst is sodium methoxide, inflammable, has corrosivity and toxicity, and reaction terminates rear product separation difficulty, product
Purity is low.Therefore, using magnetic solid base made from magnetic mg_al hydrotalcite and basic quaternary ammonium salt composite catalyzing one pot reaction
Technology synthesizes quinocetone, is easily enlarged production scale, reduces the discharge of the three wastes, filling up blank of the China in the field has
Important meaning.
(3) content of the invention
It is an object of the present invention to provide a kind of new technology of green syt quinocetone, selects magnetic made from magnetic mg_al hydrotalcite
Property solid base and basic quaternary ammonium salt composite catalyzing one pot reaction technology, reduce three waste discharge, simplify aftertreatment technology, easily
In product and industrialized production.
The technical solution adopted by the present invention is：
The present invention provides a kind of preparation method of quinocetone shown in formula (I), and methods described is：With benzo furan shown in formula (II)
Our -1- oxides, acetylacetone,2,4-pentanedione and benzaldehyde are raw material, using magnetic mg_al hydrotalcite solid base and basic quaternary ammonium salt as catalysis
Agent, using absolute ethyl alcohol as solvent, reacted 1~10 hour at 10~100 DEG C, after reaction terminates, reaction solution is post-treated to obtain formula (I)
Shown quinocetone；The basic quaternary ammonium salt is triethylbenzyl basic quaternary ammonium salt, trimethyl benzyl basic quaternary ammonium salt or tributyl
Benzyl basic quaternary ammonium salt；
Further, benzofurazan-1-oxide shown in the formula (II) and acetylacetone,2,4-pentanedione and benzaldehyde feed intake the amount of material
The ratio between be 1:1~3：1~3；The benzofurazan-1-oxide, acetylacetone,2,4-pentanedione and benzaldehyde gross mass and magnetic magnalium neatly
Stone solid base mass ratio is 1：0.05~0.2:(preferably 1：0.1), the benzofurazan-1-oxide, acetylacetone,2,4-pentanedione and benzene first
Aldehyde gross mass is 1 with basic quaternary ammonium salt quality ratio：0.05~0.2 (preferably 1：0.2)；The absolute ethyl alcohol volumetric usage is with benzo
The amount of our material of furan -1- oxides is calculated as 1~2L/mol (preferably 1L/mol).
Further, the reaction is reacted 1~10 hour at 10~50 DEG C.
Further, the magnetic mg_al hydrotalcite solid base is with Fe2+And Fe3+The ratio between amount with material 1：2 are made magnetic base
Matter, with Mg2+And Al3+Magnetic mg_al hydrotalcite solid base is prepared for raw material；Mg2+And Al3+The ratio between amount of material 2:1, magnetic substrate
Dosage is with Fe2+The gauge of material, the Fe2+With Mg2+The ratio between amount of material 1:100.Magnetic mg_al hydrotalcite magnetic of the present invention
Property solid base, be by magnalium hydrotalcite carry out magnetic modification, make it have magnetic and catalysis dual-use function, reach raising catalysis live
Property purpose, preparation method reference：The preparation of the magnetic mg_al hydrotalcite solid bases such as Zhang Haiyong is with characterizing applicating technologies the 29th
Rolled up for the 3rd phase, in March, 2002.
Further, the reaction solution post-processing approach is：Reaction terminates, reacting liquid filtering, filter cake recovery catalyst, filtrate
With charcoal absorption, stand and separate out solid, filtering, filtration cakes torrefaction obtains quinocetone shown in formula (I).
Basic quaternary ammonium salt production process bibliography (Gokel, G.W. of the present invention；Caicia,B.J.Tetrahed
ron Lett.1978,19,1743)。
The present invention is closed using magnetic solid base made from magnetic mg_al hydrotalcite and basic quaternary ammonium salt as catalyst
Into compared with the prior art, its advantage is embodied in：The application of this magnetic solid base catalyst is become relative to conventional technique
Simply, it is easy to operate, product is easily separated, and environmental pollution is small, is suitable for the industrialized production of certain scale, turns into a green
Clean synthetic route.
(4) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
With reference to：The preparation of the magnetic mg_al hydrotalcite solid bases such as Zhang Haiyong and sign applicating technologies the 3rd phases of volume 29,
In March, 2002, the preparation method of used magnetic magnalium hydrotalcite solid base of the embodiment of the present invention are as follows：(1) conjunction of magnetic substrate
Into：Using chemical coprecipitation, by Fe3+And Fe2+Sulfate or chloride press 1：1 ratio is mixed in the alkali of excess and stirred
Mixing obtains.(2) synthesis of magnetic mg_al hydrotalcite：Take a certain amount of magnetic substrate to be added in three-necked bottle, add second distillation
Water, it is stirred vigorously, 280 ± 5K of control temperature.It is 2 to take magnalium mol ratio:1 magnesium nitrate and aluminum nitrate is configured to the aqueous solution
250ml, wherein magnesium ion and aluminium ion molar concentration sum are 1.5mol/L, and magnetic substrate rubs by magnesium ion and ferrous ion
That ratio 100:1 measures.The another sodium hydroxide solution for matching somebody with somebody pH=10~13, two kinds of solution are added in reaction bulb, stirred at 110 DEG C
Mix, magnetic mg_al hydrotalcite is made in washing and drying, then forms magnetic mg_al hydrotalcite solid in 450~500 DEG C of high-temperature roastings
Alkali.
Embodiment 1
In 500 milliliters of reactors, 100 milliliters of ethanol, 13.6 grams of benzofurazan-1-oxide (0.1 mole), second are added
10 grams of acyl acetone (0.1 mole), 11 grams of benzaldehyde (0.1 mole), 1.8 grams of magnetic mg_al hydrotalcite solid base catalyst, three second
1.8 grams of base benzyl basic quaternary ammonium salt, reacted 10 hours at 30 DEG C, reaction terminates, and filters out solid base catalyst, filtrate activity
After charcoal processing, place and separate out product as light yellow solid, filtering, filtration cakes torrefaction obtains 24.2 grams of quinocetone, yield 79%.
Fusing point:204.4~204.8 DEG C (decomposition).1H NMR(400MHz,DMSO):δ:8.67 (d, J=8.4Hz, 1H),
8.59 (d, J=8.0Hz, 1H), 7.84~7.93 (m, 2H), 7.57~7.61 (m, 3H), 7.26~7.46 (m, 3H), 7.14
(d, J=16.41Hz, 1H), 2.57 (s, 3H) ppm；13C NMR(400MHz,DMSO):δ:186.13,147.66,140.11,
139.31,138.20,137.24,133.86,132.80,131.96,131.71,129.37,124.96,120.51,
14.14ppm。
Embodiment 2
In 500 milliliters of reactors, 100 milliliters of ethanol, 13.6 grams of benzofurazan-1-oxide (0.1 mole), second are added
30 grams of acyl acetone (0.3 mole), 33 grams of benzaldehyde (0.3 mole), 3.8 grams of magnetic mg_al hydrotalcite solid base catalyst, three second
3.8 grams of base benzyl basic quaternary ammonium salt, reacted 5 hours at 10 DEG C, reaction terminates, and filters out solid base catalyst, filtrate activity
After charcoal processing, place and separate out product as light yellow solid, filtering, filtration cakes torrefaction obtains 24.1 grams of quinocetone, yield 78%.
Embodiment 3
In 500 milliliters of reactors, 100 milliliters of ethanol, 13.6 grams of benzofurazan-1-oxide (0.1 mole), second are added
20 grams of acyl acetone (0.2 mole), 22 grams of benzaldehyde (0.2 mole), 6 grams of magnetic mg_al hydrotalcite solid base catalyst, triethyl group
11 grams of benzyl basic quaternary ammonium salt, reacted 1 hour at 50 DEG C, reaction terminates, and filters out solid base catalyst, filtrate is with activated carbon
After reason, place and separate out product as light yellow solid, filtering, filtration cakes torrefaction obtains 23.7 grams of quinocetone, yield 77.5%.
Embodiment 4
In 500 milliliters of reactors, 100 milliliters of ethanol, 13.6 grams of benzofurazan-1-oxide (0.1 mole), second are added
20 grams of acyl acetone (0.2 mole), 22 grams of benzaldehyde (0.2 mole), 6 grams of magnetic mg_al hydrotalcite solid base catalyst, trimethyl
11 grams of benzyl basic quaternary ammonium salt, reacted 1 hour at 50 DEG C, reaction terminates, and filters out solid base catalyst, is handled with activated carbon
Afterwards, place and separate out product as light yellow solid, filtering, filtration cakes torrefaction obtains 23.7 grams of quinocetone, yield 77.5%.
Embodiment 5
In 500 milliliters of reactors, 100 milliliters of ethanol, 13.6 grams of benzofurazan-1-oxide (0.1 mole), second are added
20 grams of acyl acetone (0.2 mole), 22 grams of benzaldehyde (0.2 mole), 6 grams of magnetic mg_al hydrotalcite solid base catalyst, tributyl
11 grams of benzyl basic quaternary ammonium salt, reacted 1 hour at 50 DEG C, reaction terminates, and filters out solid base catalyst, filtrate is with activated carbon
After reason, place and separate out product as light yellow solid, filtering, filtration cakes torrefaction obtains 24.5 grams of quinocetone, yield 80%.
Claims (5)
1. the preparation method of quinocetone shown in a kind of formula (I), it is characterised in that methods described is：With benzo furan shown in formula (II)
Our -1- oxides, acetylacetone,2,4-pentanedione and benzaldehyde are raw material, using magnetic mg_al hydrotalcite solid base and basic quaternary ammonium salt as catalysis
Agent, using absolute ethyl alcohol as solvent, reacted 1~10 hour at 10~100 DEG C, after reaction terminates, reaction solution is post-treated to obtain formula (I)
Shown quinocetone；The basic quaternary ammonium salt is triethylbenzyl basic quaternary ammonium salt, trimethyl benzyl basic quaternary ammonium salt or tributyl
Benzyl basic quaternary ammonium salt；
2. the preparation method of quinocetone as claimed in claim 1, it is characterised in that benzofuraxan -1- shown in the formula (II) is aoxidized
Feed intake the ratio between the amount of material of thing and acetylacetone,2,4-pentanedione and benzaldehyde is 1:1~3：1~3；The benzofurazan-1-oxide, acetyl
Acetone and benzaldehyde gross mass and magnetic mg_al hydrotalcite solid base mass ratio are 1:0.05~0.2, the benzofuraxan -1- oxygen
Compound, acetylacetone,2,4-pentanedione and benzaldehyde gross mass and basic quaternary ammonium salt quality ratio are 1:0.05~0.2；The absolute ethyl alcohol volume is used
Amount is calculated as 1~2L/mol with the amount of benzofurazan-1-oxide material.
3. the preparation method of quinocetone as claimed in claim 1, it is characterised in that the reaction is small in 10~50 DEG C of reactions 1~10
When.
4. the preparation method of quinocetone as claimed in claim 1, it is characterised in that the magnetic mg_al hydrotalcite solid base is with Fe2+
And Fe3+The ratio between amount with material 1：2 are made magnetic substrate, with Mg2+And Al3+Magnetic mg_al hydrotalcite solid base is prepared for raw material；
Mg2+And Al3+The ratio between amount of material 2:1, magnetic substrate dosage is with Fe2+The gauge of material, the Fe2+With Mg2+The amount of material it
Than 1:100.
5. the preparation method of quinocetone as claimed in claim 1, it is characterised in that the reaction solution post-processing approach is：Reaction knot
Beam, reacting liquid filtering, filter cake recovery catalyst, filtrate charcoal absorption stand and separate out solid, filtering, and filtration cakes torrefaction obtains formula
(I) quinocetone shown in.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157603A (en) * | 2007-11-02 | 2008-04-09 | 浙江工业大学 | Environment-friendly method for synthesizing acetylacetone |
| CN102329272A (en) * | 2011-11-01 | 2012-01-25 | 荆州市新元生物科技有限公司 | Method for preparing quinocetone |
| CN102372678A (en) * | 2010-08-24 | 2012-03-14 | 许吉冲 | Feed additive quinocetone and preparation method thereof |
| CN102911084A (en) * | 2012-09-25 | 2013-02-06 | 浙江工业大学 | Preparation method of tert-butyl carbazate |
| CN104045503A (en) * | 2014-05-26 | 2014-09-17 | 中国科学院广州能源研究所 | Method for preparing C10-C18 long chain naphthenic hydrocarbon by utilizing furfural compound |
| CN104672155A (en) * | 2013-12-03 | 2015-06-03 | 中牧实业股份有限公司黄冈动物药品厂 | Synthetic method of improved quinocetone |
-
2015
- 2015-11-19 CN CN201510801547.6A patent/CN105294581B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157603A (en) * | 2007-11-02 | 2008-04-09 | 浙江工业大学 | Environment-friendly method for synthesizing acetylacetone |
| CN102372678A (en) * | 2010-08-24 | 2012-03-14 | 许吉冲 | Feed additive quinocetone and preparation method thereof |
| CN102329272A (en) * | 2011-11-01 | 2012-01-25 | 荆州市新元生物科技有限公司 | Method for preparing quinocetone |
| CN102911084A (en) * | 2012-09-25 | 2013-02-06 | 浙江工业大学 | Preparation method of tert-butyl carbazate |
| CN104672155A (en) * | 2013-12-03 | 2015-06-03 | 中牧实业股份有限公司黄冈动物药品厂 | Synthetic method of improved quinocetone |
| CN104045503A (en) * | 2014-05-26 | 2014-09-17 | 中国科学院广州能源研究所 | Method for preparing C10-C18 long chain naphthenic hydrocarbon by utilizing furfural compound |
Non-Patent Citations (7)
| Title |
|---|
| A new Route for the Synthesis of Phenazine Di-N-Oxides;M.S.Abd EI-Halim，等;《Monatshefte fur Chemie》;19951231;第126卷;第1217-1223页 * |
| 喹烯酮合成工艺的改进;唐树和，等;《化学通报》;20090430(第4期);第381-383页 * |
| 磁性水滑石的合成及性能的研究;冶正得;《石油化工应用》;20140228;第33卷(第2期);第86-89页 * |
| 磁性镁铝水滑石固体碱催化苯甲醛与丙二酸二乙酯的反应;张海永，等;《应用科技》;20020228;第29卷(第2期);第50-52页 * |
| 磁性镁铝水滑石固体碱的制备与表征;张海永，等;《应用科技》;20020331;第29卷(第3期);第61-63页 * |
| 超声辐射下n(Mg)∶n(Al)水滑石催化合成二硝基查尔酮的研究;巢芳家，等;《工业催化》;20071231;第15卷(第12期);第39-42页 * |
| 金属氧化物固体碱在有机合成中的应用;裴文，等;《有机化学》;20100930;第30卷(第9期);第1410-1418页 * |
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