CN1034169C - Synthesis method for trimethoxybenz-aldehyde - Google Patents
Synthesis method for trimethoxybenz-aldehyde Download PDFInfo
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- CN1034169C CN1034169C CN91106192A CN91106192A CN1034169C CN 1034169 C CN1034169 C CN 1034169C CN 91106192 A CN91106192 A CN 91106192A CN 91106192 A CN91106192 A CN 91106192A CN 1034169 C CN1034169 C CN 1034169C
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- tripotassium iron
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- iron hexacyanide
- exchange resin
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Abstract
The present invention relates to a synthetic method for trimethoxy benzaldehyde by oxidizing trimethoxy benzhydrazide. Solid acid (ion exchange resin or molecular sieve, etc.) is taken as a catalyst and a mono-oxygen donor is taken as an oxygen source (mainly hydrogen peroxide) to make potassium ferricyanide of an oxidizing agent in the reaction circularly used. Compared with the potassium hypermanganate oxidizing method used at present, the technology method can effectively avoid the environmental pollution of by products, enhance the utilization rate of the oxidizing agent and simplify the production technology. Simultaneously, the production cost can be greatly reduced. The present invention is suitable for industrial production.
Description
The present invention relates to the preparation method of organic compound TMB, specifically, make this reaction process be more suitable in industrial production, adopting for providing a kind of new catalyst system for the reaction of raw material synthesizing trimethoxy phenyl aldehyde by the trimethoxy benzoyl hydrazine.
TMB is important Organic Chemicals, and wherein a kind of preparation method is by trimethoxy benzoyl hydrazine Tripotassium iron hexacyanide oxidation synthesizing trimethoxy phenyl aldehyde, and oxygenant is reduced into yellow prussiate of potash, and reaction process can be expressed as:
Reaction (1) needs a large amount of Tripotassium iron hexacyanides, recycles for making oxygenant, and the yellow prussiate of potash that reaction must be obtained is reoxidised into the Tripotassium iron hexacyanide.The method of industrial common employing at present is to utilize potassium permanganate to be oxygenant, finishes the reversed reaction of above-mentioned reaction (2), and potassium permanganate is reduced into Manganse Dioxide simultaneously, and the following formula reaction promptly takes place:
But adopt above-mentioned potassium permanganate oxidation process, will produce a large amount of by product Manganse Dioxide mud, and normal entrained iron potassium cyanide can't separate in the mud, not only increases production cost, Manganse Dioxide mud also causes serious pollution to environment simultaneously.
Other has reported in literature (Hung, Teljes Hu23,214 (1980)) can take hydrogen peroxide is oxygenant, finishes the oxidizing reaction of yellow prussiate of potash, but must add sulfuric acid, the following reaction of its reaction process (4):
Because reaction (1) is oxygen source with the hydrogen peroxide, resultant of reaction is that water can not cause any pollution, has solved and has utilized potassium permanganate to be oxygenant, produces the shortcoming that a large amount of Manganse Dioxide mud can't be handled.But, the inorganic acid radical (sulfate radical) that adds easily with Tripotassium iron hexacyanide reaction form vitriolate of tartar or with reaction in ammoniacal liquor formation ammonium sulfate, its amount can constantly increase in Tripotassium iron hexacyanide circulation, and it and water solubility are very big, be difficult to crystallization or it separated, will influence the normal reaction of reaction (1) with other method.Therefore this method is still had any problem in industrial practical application.
The objective of the invention is to overcome the oxygenant Tripotassium iron hexacyanide in the above-mentioned preparation TMB method and recycle the various shortcomings that process produces, for the circulation of this oxygenant provides a kind of new catalyst system, and then provide a kind of synthetic method that is more suitable for the preparation TMB that industrial production adopts.
The synthetic method of TMB of the present invention remains utilizes the Tripotassium iron hexacyanide that utilizes of present industrial employing the trimethoxy benzoyl hydrazine to be oxidized to the synthetic method (reaction (1)) of TMB for oxygenant, again oxygenant is recycled simultaneously, promptly shown in the reaction (2) yellow prussiate of potash is reoxidised into the Tripotassium iron hexacyanide, recycles then and finish reaction (1).But adopt catalytic oxidation for finishing reaction (2) the present invention, it reacts following reaction (5):
Used oxygen source adopts single oxygen donor, NaOCl for example, H
2O
2, or ROOH etc.Catalyzer adopt proton can be provided solid acid (ion exchange resin, molecular sieve or other solid acid) for example, cation polystyrene sulfonic resin, large pores cation exchange resin, faujusite, ZSM-5 zeolite or mordenite etc.Preferable oxygenant is a hydrogen peroxide in above-mentioned oxygen source, and its reduzate can not produce any pollution, does not also need to handle again.And the catalyst ion exchange resin, molecular sieve or other solid acid need carry out ion-exchange before use, make hydrogen ion exchange resin or hydrogen type molecular sieve or other Hydrogen solid acid.Reaction is after (5) carry out, the solid acid that uses can exchange (the hydrogen ion switching method can utilize common operating process to carry out) with hydrogen ion again, can realize the activating and regenerating of catalyzer, thereby can use repeatedly.Reaction (5) can be carried out at normal temperatures smoothly under above-mentioned oxygen source of adding and catalyzer condition.Improve temperature of reaction,, add the oxygenant decomposition but easily make, for H with fast reaction speed
2O
2Make the oxygen source temperature of reaction and can be controlled in 15～50 ℃, preferable temperature of reaction is 25～40 ℃.For guaranteeing that yellow prussiate of potash fully is oxidized to the Tripotassium iron hexacyanide, should be not less than 1～3 times of Theoretical Calculation amount that gets electronic number by iron ion dead electricity subnumber and oxygen source in the yellow prussiate of potash as the addition of oxygen source.Should add excessive solid acid catalyst simultaneously, with the hydrogen ion that guarantees to provide necessary.Below by example technology of the present invention is further described.
Example 1, TMB synthetic 1
In 250ml there-necked flask (band condenser, thermometer and charging opening), add Tripotassium iron hexacyanide 18g (0.054mol), add water 100ml dissolving.Add benzene 60～100ml, ammoniacal liquor 5～30ml and trimethoxy benzoyl hydrazine 5.7g (0.0252mol), 10～40 ℃ of controlled temperature, reaction is 2 hours under magnetic stirrer stirs.Separate organic phase (toluene phase) with separating funnel reaction back, be washed till neutrality with 3%HCl and 3%NaOH after, carry out underpressure distillation and remove toluene and get product TMB 4.10g, yield is 83.1%, molten point is 70～72 ℃.NH is removed in the water underpressure distillation
4OH adds HY zeolite (the HY zeolite is made the HY zeolite by the NaY zeolite through ion-exchange, Na ion residues＜2%) 6g, 30% hydrogen peroxide 10g, 0～60 ℃ of stirring reaction 2 hours, remove by filter zeolite, obtained aqueous solution can continue to do oxygenant to be used for reaction (1).Zeolite catalyst carries out ion-exchange and makes the HY zeolite and reuse.
Example 2, yellow prussiate of potash oxidizing reaction
Press example 1 described reaction, when NH is removed in the water underpressure distillation
4Behind the OH, the ion exchange resin of hydrogenation ion-exchange 15 grams, other condition can be produced potassium ferricyanide solution for reaction (1) use as described in the example 1.The catalyst ion exchange resin with acid exchange hydrogen ion exchange resin, reuse again.
Example 3, Tripotassium iron hexacyanide work-ing life
By example 1 described reaction (1) condition system TMB and example 2 described reactions (5) oxygenant is carried out oxidation as the Tripotassium iron hexacyanide of testing usefulness for the second time, reuse behind the catalyst regeneration, the yield that gets the product TMB is listed in the table below.
Table 1 Tripotassium iron hexacyanide recycles the life-span
| Experiment | Trimethoxy benzoyl hydrazine (g) | Tripotassium iron hexacyanide add-on (g) | Ion exchange resin (g) | Hydrogen peroxide (g) | TMB (g) | Aldehyde yield % |
| 1 2 3 4 5 6 | 25.2 25.2 25.2 25.2 25.2 25.2 | Mend 7.2 benefits, 8.6 benefits 6.8 72.0 mend 7.2 | " " reused in 140 regeneration backs " | 20.0 18.9 22.4 24.0 21.2 | 18.1 16.4 16.0 14.8 15.6 16.2 | 83.3 75.1 73.6 67.7 71.4 74.1 |
Adopt catalyst system of the present invention by above-mentioned example, catalyzer can recycle repeatedly, adds people's oxygen source (hydrogen peroxide) reaction and easily carries out, and product need not handled no any pollution, and the loss of the simultaneous oxidation agent Tripotassium iron hexacyanide is few.Utilize method of the present invention to prepare the trimethoxy benzoyl, not only production technique is simple, can eliminate the pollution to environment, can reduce production costs by a relatively large margin again.
Claims (3)
1. an employing Tripotassium iron hexacyanide is an oxygenant, by the synthetic method of trimethoxy benzoyl hydrazine through oxidation system TMB, it is characterized in that the yellow prussiate of potash that generates behind the oxidant reaction is to adopt catalytic oxidation to make it be reoxidised into the Tripotassium iron hexacyanide, used oxygen source adopts single oxygen donor, comprise NaOCl, H
2O
2Or ROOH; Catalyzer adopts the solid acid that proton can be provided: ion exchange resin or molecular sieve.
2. according to the described synthetic method of claim 1, it is characterized in that solid acid can adopt the cation polystyrene sulfonic resin, large pores cation exchange resin, faujusite, ZSM-5 zeolite or mordenite.
3. according to the described synthetic method of claim 1, it is characterized in that yellow prussiate of potash is oxidized to the oxidizing reaction of the Tripotassium iron hexacyanide, oxygen source adopts hydrogen peroxide, and temperature of reaction is 25～40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91106192A CN1034169C (en) | 1991-07-30 | 1991-07-30 | Synthesis method for trimethoxybenz-aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91106192A CN1034169C (en) | 1991-07-30 | 1991-07-30 | Synthesis method for trimethoxybenz-aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069020A CN1069020A (en) | 1993-02-17 |
| CN1034169C true CN1034169C (en) | 1997-03-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91106192A Expired - Fee Related CN1034169C (en) | 1991-07-30 | 1991-07-30 | Synthesis method for trimethoxybenz-aldehyde |
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| CN110627126A (en) * | 2019-10-24 | 2019-12-31 | 福州大学 | Preparation and application of self-supporting ultrathin two-dimensional flower-shaped manganese oxide nanosheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56150034A (en) * | 1980-04-24 | 1981-11-20 | Ube Ind Ltd | Preparation of 3,4,5-trimethoxybenzaldehyde |
| RO90634A2 (en) * | 1984-10-15 | 1986-12-10 | Institutul De Chimie,Ro | PROCESS FOR PREPARATION OF DIETHYLENE AND TRIMETOXIBENZELDEHYDES |
| CN1038636A (en) * | 1988-06-25 | 1990-01-10 | 南京药物研究所 | 3,4,5-TMB new synthesis method |
-
1991
- 1991-07-30 CN CN91106192A patent/CN1034169C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56150034A (en) * | 1980-04-24 | 1981-11-20 | Ube Ind Ltd | Preparation of 3,4,5-trimethoxybenzaldehyde |
| RO90634A2 (en) * | 1984-10-15 | 1986-12-10 | Institutul De Chimie,Ro | PROCESS FOR PREPARATION OF DIETHYLENE AND TRIMETOXIBENZELDEHYDES |
| CN1038636A (en) * | 1988-06-25 | 1990-01-10 | 南京药物研究所 | 3,4,5-TMB new synthesis method |
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| Publication number | Publication date |
|---|---|
| CN1069020A (en) | 1993-02-17 |
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