CN103524313B - 3,5-dimethylbenzaldehyde preparation method - Google Patents
3,5-dimethylbenzaldehyde preparation method Download PDFInfo
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- CN103524313B CN103524313B CN201310462540.7A CN201310462540A CN103524313B CN 103524313 B CN103524313 B CN 103524313B CN 201310462540 A CN201310462540 A CN 201310462540A CN 103524313 B CN103524313 B CN 103524313B
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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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
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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
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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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention discloses a 3,5-dimethylbenzaldehyde preparation method. The method comprises the steps of mixing, dissolving, reacting, reduced pressure distillation and the like, and allows 3,5-dimethylbenzaldehyde to be prepared through the selective oxidation of mesitylene via the catalytic oxidation effect of a cobalt salt and the coordination effect of a brominated quaternary ammonium salt. The method realizes high raw material conversion rate, high product selectivity, environmentally-friendly reaction process because of the utilization of oxygen as an oxygen source, and high process security because of a reaction pressure being normal pressure or a low pressure. Additionally, the above synthesis method has the advantages of simplicity, simple technologic operation, high yield and low cost.
Description
Technical field
The invention belongs to catalyzed oxidation field, 3,5-dimethylbenzaldehyde prepared by the cobalt salt catalyzed oxidation sym-trimethylbenzene being specially part participation.
Background technology
3,5-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehydes, 2,5-dimethylbenzaldehydes and 2,6-dimethylbenzaldehyde is all important fine-chemical intermediate, all can be applicable to synthesize transparent nucleator for polypropylene, is the non-toxic plastic auxiliary agent of a new generation, is widely used in packaging material for food production.The transparent nucleator for polypropylene that 3,5-dimethylbenzaldehyde is synthesized is best performance in fineness of grain, plastic, transparent, and therefore the synthesis exploitation of 3,5-dimethylbenzaldehydes comes into one's own.
To so far, 3, the 5-dimethylbenzaldehyde main preparation methods at home and abroad reported in document and patent have: electrolytic synthesis, organic chemical synthesis method and biological synthesis process.
Electrolytic synthesis adopts sym-trimethylbenzene at value Mn (Mn
4+, Mn
3+) oxidation under, be aldehyde radical (-CHO) by one of them methyl oxidation, thus obtain 3,5-dimethylbenzaldehyde, the effect of electricity realizes at a low price manganese (Mn
2+) be oxidized to value Mn, to ensure recycling of value Mn.
Organic chemical synthesis method is with alcohol, dimethylbenzene, trimethylbenzene and acid etc. for raw material, through catalyzed oxidation or reduction synthesis 3,5-dimethylbenzaldehyde.More successfully wherein take sym-trimethylbenzene as the chloromethylation process of raw material.
Biological synthesis process be with fungi or bacterium for catalytic oxidant, alcohol or sym-trimethylbenzene etc. are oxidized to 3,5-dimethylbenzaldehyde.
All there are certain relative merits in aforesaid method, realize suitability for industrialized production and still have any problem.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide the preparation method of 3, the 5-dimethylbenzaldehydes that a kind of preparation method is simple, economical and efficient, transformation efficiency and selectivity are high.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of preparation method of 3,5-dimethylbenzaldehyde, is characterized in that, comprise the following steps:
(1) mix: in the reactor, add divalent cobalt and Quaternary ammonium bromide, at room temperature stir, the ratio of the amount of substance that described divalent cobalt and Quaternary ammonium bromide add is 1:0.5-10;
(2) dissolve: under the stirring velocity of 400 turns/min, add sym-trimethylbenzene, in the amount of substance of divalent cobalt for 1mol, the add-on of described sym-trimethylbenzene is 1.4-28L, then, solution is heated to 80-110 DEG C, and stirs 20-60min and all dissolve to divalent cobalt and Quaternary ammonium bromide;
(3) react: in the solution described in step (2), pass into oxygen at ambient pressure, and react 8-24h under the temperature condition of 60-160 DEG C; Or being transferred to by the solution described in step (2) is equipped with in the autoclave pressure of magnetic stirrer,
<with after replacement of oxygen at least twice under the pressure condition of 0.5Mpa, under remaining on the temperature condition of 60-160 DEG C, react 8-24h;
(4) underpressure distillation: be greater than 10 by adding alkali lye regulator solution pH value after reacted for step (3) solution cooling, then Separation of Water oil two-phase, and oil reservoir is through washing, dry, underpressure distillation, and collects 115-125
othe cut of C/20mmHg, obtains 3,5-dimethylbenzaldehyde.
Wherein, described divalent cobalt is CoCl
2.6H
2o or Co (OAc)
2, and described divalent cobalt consumption is 0.5 mol% ~ 10 mol% of sym-trimethylbenzene amount.
Further, the general formula of described Quaternary ammonium bromide is R
1r
2r
3r
4n
+br, wherein said R are alkyl or aryl, and described Quaternary ammonium bromide consumption is 0.5 mol% ~ 20 mol% of sym-trimethylbenzene amount.
Any one and described Quaternary ammonium bromide is Tetrabutyl amonium bromide, four octyl group brometo de amonios, in didecyldimethylammonium bromide.
In described step (3), when starting to pass into, the speed that passes into of oxygen is 0.5L/min, and after question response causes, the speed that passes into of oxygen is 1L/min.
And the alkali lye described in step (4) is concentration is 1 mol/L sodium hydroxide solution.
The invention has the beneficial effects as follows: present invention achieves the higher conversion of raw material and the highly selective of product, and owing to utilizing oxygen for oxygen source, make reaction process environmental protection, and reaction pressure is normal pressure or low pressure, so process safety is high, in addition, simple synthetic method of the present invention, technological operation is simple, and productive rate is high, and cost is low.
Embodiment
Below in conjunction with specific embodiment, concrete introduction is carried out to the present invention.
embodiment 1:
A kind of preparation method of 3,5-dimethylbenzaldehyde, comprises the following steps:
(1) mix: in the reactor, add CoCl
2.6H
2o(1 mol%) and TBAB(Tetrabutyl amonium bromide, 1mol%), at room temperature stir;
(2) dissolve: under the stirring velocity of 400 turns/min, add sym-trimethylbenzene 400ml, then, solution is heated to 110 DEG C, and stir 30min and all dissolve to divalent cobalt and Quaternary ammonium bromide;
(3) react: in the solution described in step (2), pass into oxygen with 0.5L/min flow velocity at ambient pressure, after question response causes, flow velocity increases to 1L/min, and reacts 11h under the temperature condition of 110-120 DEG C;
(4) underpressure distillation: be that the sodium hydroxide solution regulator solution pH value of 1 mol/L is greater than 10, then Separation of Water oil two-phase by adding concentration after the cooling of reacted for step (3) solution, and oil reservoir is through washing, dry, underpressure distillation, and collect 115-125
othe cut of C/20mmHg, obtains 3,5-dimethylbenzaldehyde.
The product purity that embodiment 1 prepares is 99%, and reaction conversion ratio 40%, selectivity 72%, separation yield 25%.
Product characterizes:
1h NMR (CDCl
3)
δ9.94 (s, 1H ,-CHO), 7.43 (s, 2H, Ar-H), 7.22 (s, 1H, Ar-H), 2.49 (s, 6H ,-CH
3).
embodiment 2:
A kind of preparation method of 3,5-dimethylbenzaldehyde, comprises the following steps:
(1) mix: in the reactor, add CoCl
2.6H
2o(1 mol%) and TBAB (Tetrabutyl amonium bromide, 1 mol%), at room temperature stir;
(2) dissolve: under the stirring velocity of 400 turns/min, add sym-trimethylbenzene 20ml, then, solution is heated to 110 DEG C, and stir 30min and all dissolve to divalent cobalt and Quaternary ammonium bromide;
(3) react: the solution described in step (2) is transferred in the autoclave pressure of the 100ml that magnetic stirrer is housed, with replacement of oxygen twice under the pressure condition of 0.3 MPa, and reacts 12h under remaining on the temperature condition of 110 DEG C.
(4) underpressure distillation: be that the sodium hydroxide solution regulator solution pH value of 1 mol/L is greater than 10, then Separation of Water oil two-phase by adding concentration after the cooling of reacted for step (3) solution, and oil reservoir is through washing, dry, underpressure distillation, and collect 115-125
othe cut of C/20mmHg, obtains 3,5-dimethylbenzaldehyde.
The product purity that embodiment 2 prepares is 99%, and reaction conversion ratio 84%, selectivity 73%, separation yield 52%.
embodiment 3:
A kind of preparation method of 3,5-dimethylbenzaldehyde, comprises the following steps:
(1) mix: in the reactor, add Co (OAc)
2(1 mol%) and TOAB (four octyl group brometo de amonios, 2 mol%), at room temperature stir;
(2) dissolve: under the stirring velocity of 400 turns/min, add sym-trimethylbenzene 400ml, then, solution is heated to 80 DEG C, and stir 30min and all dissolve to divalent cobalt and Quaternary ammonium bromide;
(3) react: in the solution described in step (2), pass into oxygen with 0.5L/min flow velocity at ambient pressure, after question response causes, flow velocity increases to 1L/min, and reacts 12h under the temperature condition of 80 DEG C;
(4) underpressure distillation: be that the sodium hydroxide solution regulator solution pH value of 1 mol/L is greater than 10, then Separation of Water oil two-phase by adding concentration after the cooling of reacted for step (3) solution, and oil reservoir is through washing, dry, underpressure distillation, and collect 115-125
othe cut of C/20mmHg, obtains 3,5-dimethylbenzaldehyde.
The product purity that embodiment 3 prepares is 99%, and reaction conversion ratio is 20%, selectivity 97%, yield 18%.
embodiment 4:
A kind of preparation method of 3,5-dimethylbenzaldehyde, comprises the following steps:
(1) mix: in the reactor, add Co (OAc)
2(1 mol%) and DDAB (didecyldimethylammonium bromide, 1.5 mol%), at room temperature stir;
(2) dissolve: under the stirring velocity of 400 turns/min, add sym-trimethylbenzene 400ml, then, solution is heated to 80 DEG C, and stir 30min and all dissolve to divalent cobalt and Quaternary ammonium bromide;
(3) react: in the solution described in step (2), pass into oxygen with 0.5L/min flow velocity at ambient pressure, after question response causes, flow velocity increases to 1L/min, and reacts 12h under the temperature condition of 80 DEG C;
(4) underpressure distillation: be that the sodium hydroxide solution regulator solution pH value of 1 mol/L is greater than 10, then Separation of Water oil two-phase by adding concentration after the cooling of reacted for step (3) solution, and oil reservoir is through washing, dry, underpressure distillation, and collect 115-125
othe cut of C/20mmHg, obtains 3,5-dimethylbenzaldehyde.
The product purity that embodiment 4 prepares is 99%, and reaction conversion ratio 78%, selectivity 81%, yield 51%.
embodiment 5
A kind of preparation method of 3,5-dimethylbenzaldehyde, comprises the following steps:
(1) mix: Co (OAc)
2(1 mol%) and DDAB (didecyldimethylammonium bromide, 1.5 mol%), at room temperature stir;
(2) dissolve: under the stirring velocity of 400 turns/min, add sym-trimethylbenzene 20ml, then, solution is heated to 110 DEG C, and stir 30min and all dissolve to divalent cobalt and Quaternary ammonium bromide;
(3) react: the solution described in step (2) is transferred in the autoclave pressure of the 100ml that magnetic stirrer is housed, with replacement of oxygen twice under the pressure condition of 0.2MPa, and reacts 12h under remaining on the temperature condition of 110 DEG C.
(4) underpressure distillation: be that the sodium hydroxide solution regulator solution pH value of 1 mol/L is greater than 10, then Separation of Water oil two-phase by adding concentration after the cooling of reacted for step (3) solution, and oil reservoir is through washing, dry, underpressure distillation, and collect 115-125
othe cut of C/20mmHg, obtains 3,5-dimethylbenzaldehyde.
The product purity that embodiment 5 prepares is 99%, and reaction conversion ratio 89%, selectivity 83%, separation yield 70%.
Other embodiment results are as shown in table 1:
Table 1:
3,5-dimethylbenzaldehyde prepared by cobalt salt under normobaric oxygen atmosphere-Quaternary ammonium bromide catalyzed oxidation sym-trimethylbenzene:
| Sequence number | Catalyzer | Part | Temperature | Selectivity | Yield |
| 1 | CoCl 2· 6H 2O(1.0mol%) | TBAB(0.5mol%) | 120℃ | 61% | 47% |
| 2 | CoCl 2· 6H 2O(1.0mol%) | TBAB(1.0mol%) | 120℃ | 74% | 56% |
| 3 | CoCl 2· 6H 2O(1.0mol%) | TBAB(2.0mol%) | 120℃ | 82% | 59% |
| 4 | CoCl 2· 6H 2O(1.0mol%) | TBAB(3.0mol%) | 120℃ | 83% | 42% |
| 5 | CoCl 2· 6H 2O(0.5mol%) | TBAB(1.0mol%) | 120℃ | 79% | 46% |
| 6 | CoCl 2· 6H 2O(1.5mol%) | TBAB(3.0mol%) | 120℃ | 78% | 52% |
| 7 | CoCl 2· 6H 2O(2.0mol%) | TBAB(4.0mol%) | 120℃ | 84% | 63% |
| 8 | CoCl 2· 6H 2O(1.0mol%) | TBAB(2.0mol%) | 60℃ | 0 | 0 |
| 9 | CoCl 2· 6H 2O(1.0mol%) | TBAB(2.0mol%) | 80℃ | 0 | 0 |
| 10 | CoCl 2· 6H 2O(1.0mol%) | TBAB(2.0mol%) | 100℃ | 90% | 10% |
| 11 | CoCl 2· 6H 2O(1.0mol%) | TBAB(2.0mol%) | 140℃ | 55% | 49% |
| 12 | CoCl 2· 6H 2O(1.0mol%) | TBAB(2.0mol%) | 160℃ | 23% | 26% |
| 13 | CoBr 2· 6H 2O(1.0mol%) | TBAB(2.0mol%) | 120℃ | 69% | 58% |
| 14 | CoCl 2· 6H 2O(1.0mol%) | NH 4Br(2.0mol%) | 120℃ | 57% | 40% |
| 15 | CoCl 2· 6H 2O(1.0mol%) | Didodecyldimethylammbromide bromide (2.0mol%) | 120℃ | 73% | 35% |
| 16 | CoCl 2· 6H 2O(1.0mol%) | DDA (2.0mol%) | 120℃ | 64% | 46% |
| 17 | CoCl 2· 6H 2O(1.0mol%) | Four octyl group brometo de amonios | 120℃ | 75% | 48% |
| 18 | CoCl 2· 6H 2O(1.0mol%) | 4 bromide | 120℃ | 70% | 23% |
| 19 | CoCl 2· 6H 2O(1.0mol%) | Tetramethyl ammonium chloride | 120℃ | 74% | 9% |
From embodiment 1-5 and table 1: prepare 3,5-dimethylbenzaldehyde is colourless or light yellow transparent liquid, there is almond, purity is 99%, its boiling point 221 ~ 223 DEG C, fusing point 9 ~ 10 DEG C is 1.017g/ml the relative densities of 20 DEG C, and achieve the higher conversion of raw material and the highly selective of product, and owing to utilizing oxygen for oxygen source, make reaction process environmental protection, and reaction pressure is normal pressure or low pressure, so process safety is high, in addition, simple synthetic method of the present invention, technological operation is simple, productive rate is high, and cost is low.
The present invention is illustrated according to above-described embodiment, should be appreciated that above-described embodiment does not limit the present invention in any form, and all employings are equal to replacement or the technical scheme that obtains of equivalent transformation mode, all drop within protection scope of the present invention.
Claims (5)
1. the preparation method of a dimethylbenzaldehyde, is characterized in that, comprises the following steps:
(1) mix: in the reactor, add divalent cobalt and Quaternary ammonium bromide, at room temperature stir; The general formula of described Quaternary ammonium bromide is R
1r
2r
3r
4n
+br, wherein said R is alkyl, and with the amount of substance of substrate sym-trimethylbenzene for benchmark, the consumption of divalent cobalt is 0.5 mol% ~ 10 mol%, and the consumption of Quaternary ammonium bromide is 0.5 mol% ~ 20 mol%, the ratio of the amount of substance that divalent cobalt and Quaternary ammonium bromide add is 1:0.5-10;
(2) dissolve: under the stirring velocity of 400 turns/min, add sym-trimethylbenzene, in the amount of substance of divalent cobalt for 1mol, the add-on of described sym-trimethylbenzene is 1.4-28L, then, solution is heated to 80-110 DEG C, and stirs 20-60min and all dissolve to divalent cobalt and Quaternary ammonium bromide;
(3) react: in the solution described in step (2), pass into oxygen at ambient pressure, and react 8-24h under the temperature condition of 60-160 DEG C; Or being transferred to by the solution described in step (2) is equipped with in the autoclave pressure of magnetic stirrer,
<with after replacement of oxygen at least twice under the pressure condition of 0.5Mpa, under remaining on the temperature condition of 60-160 DEG C, react 8-24h;
(4) underpressure distillation: be greater than 10 by adding alkali lye regulator solution pH value after reacted for step (3) solution cooling, then Separation of Water oil two-phase, and oil reservoir is through washing, dry, underpressure distillation, and collects 115-125
othe cut of C/20mmHg, obtains 3,5-dimethylbenzaldehyde.
2. the preparation method of a kind of 3,5-dimethylbenzaldehydes according to claim 1, is characterized in that, described divalent cobalt is CoCl
2.6H
2o or Co (OAc)
2, and the consumption of described divalent cobalt is 0.5 mol% ~ 10 mol% of sym-trimethylbenzene amount.
3. according to claim 1 and 2 a kind of 3, the preparation method of 5-dimethylbenzaldehyde, it is characterized in that, described Quaternary ammonium bromide is Tetrabutyl amonium bromide, four octyl group brometo de amonios, any one in didecyldimethylammonium bromide, 4 bromide, didodecyldimethylammbromide bromide.
4. the preparation method of a kind of 3,5-dimethylbenzaldehydes according to claim 1 and 2, is characterized in that, in described step (3), when starting to pass into, the speed that passes into of oxygen is 0.5L/min, and after question response causes, the speed that passes into of oxygen is 1L/min.
5. the preparation method of a kind of 3,5-dimethylbenzaldehydes according to claim 1 and 2, is characterized in that, described alkali lye is concentration is 1 mol/L sodium hydroxide solution.
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| CN105753672A (en) * | 2016-03-31 | 2016-07-13 | 常州大学 | Synthesis method for 3,5-dimethyl benzaldehyde |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3732314A (en) * | 1970-12-07 | 1973-05-08 | Universal Oil Prod Co | Preparation of aromatic aldehydes |
-
2013
- 2013-10-08 CN CN201310462540.7A patent/CN103524313B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3732314A (en) * | 1970-12-07 | 1973-05-08 | Universal Oil Prod Co | Preparation of aromatic aldehydes |
Non-Patent Citations (3)
| Title |
|---|
| liquid phase oxidation of mesitylene to 3,5-dimethyl-benzaldehyde;Gabriela valehrachova et al.;《Collection Czechoslovak Chern. Commun.》;19861231;第51卷;2574-2581 * |
| THE EFFECT OF ACETATES ON THE ACTIVITY OF COBALT BROMIDE CATALYSTS*;Milan HRONEC et al.,;《Collection Czechoslov. Chem. Commun》;19791231;第44卷;3362-3372 * |
| 刘生丽等.3,5-二甲基苯甲醛的国内外研究进展.《甘肃石油和化工》.2012,(第3期),18-22. * |
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