CN106146286A - The preparation method of 4,4 ' biphenyl dicarboxylic acids - Google Patents
The preparation method of 4,4 ' biphenyl dicarboxylic acids Download PDFInfo
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- CN106146286A CN106146286A CN201610492195.5A CN201610492195A CN106146286A CN 106146286 A CN106146286 A CN 106146286A CN 201610492195 A CN201610492195 A CN 201610492195A CN 106146286 A CN106146286 A CN 106146286A
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- biphenyl dicarboxylic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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Abstract
The invention discloses a kind of 4, the preparation method of 4 ' biphenyl dicarboxylic acids, it is by 4,4 ' the oxidized reactions of diphenyl-dimethanal obtain, wherein, the oxidant that oxidation reaction uses is sodium chlorite, sodium chlorite and 4, the mol ratio of 4 ' diphenyl-dimethanals is 2: 1～4: 1, the organic solvent that oxidation reaction uses is water, methyl alcohol, ethanol or dichloromethane, and the temperature of oxidation reaction is 0～5 DEG C, and oxidation reaction is also added with sulfamic acid or dimethyl sulfoxide, sulfamic acid or dimethyl sulfoxide and 4, the mol ratio of 4 ' diphenyl-dimethanals is 0.5: 1～2: 1.The method reaction condition of the present invention is gentle, and security is higher, and production cost is relatively low, and especially oxidation reaction yield is higher, good product quality, and environmental pollution is little, thus is suitable for industrialized production.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of 4, the preparation side of 4 '-biphenyl dicarboxylic acid
Method.
Background technology
4,4 '-biphenyl dicarboxylic acid is important organic synthesis intermediate, (such as has resistance at pharmacy, organic synthesis macromolecule
The combustion polyurethane of performance or polyesters macromolecule) and supramolecular materials and liquid crystal material in be widely used.
At present, synthesizing 4 with biphenyl for initiation material, the method for 4 '-biphenyl dicarboxylic acid mainly has a following two:
(1) with biphenyl as initiation material, target product is obtained through alkylation and oxidation.The method alkylated reaction yield is low,
Poor selectivity, thus cause intermediate 4,4 '-dimethyl diphenyl market price is higher；And the method oxidizing process is often attended by
Decarboxylic reaction, thus be not suitable for industrialized production.
(2) with biphenyl as initiation material, first 4,4 '-two (chloromethyl) biphenyl is generated through chloromethylation, then through Sommelet
Reaction generation 4,4 '-diphenyl-dimethanal, finally oxidized obtain target product (see document " 4, the conjunction of 4 '-biphenyl dicarboxylic acid
Become ", Ge Hongyu etc., Lanzhou University of Science & Technology's journal, the 3rd phase of volume 33, page 69～71, in June, 2007).
Oxidation reaction in above-mentioned (2nd) kind method is that 4,4 '-diphenyl-dimethanal and four butyl bromation amine are joined ice
It acetic acid is heated with stirring to 80 DEG C and slowly drips hydrogen peroxide at such a temperature, dripping off stirring reaction at a temperature of 80～85 DEG C
8h, post-treated obtains 4, and 4 '-biphenyl dicarboxylic acid, the method yield is 80.4%.The deficiency of this oxidation reaction is: (1) yield
Relatively low, only about 80%.(2) using hydrogen peroxide to have certain danger under hot conditions, especially this reaction time is relatively
Long, further increase danger, security is relatively low.(3) need to use the phase transfer catalyst that price is higher, cause producing into
This is higher.(4) above-mentioned deficiency causes the method to be not suitable for industrialized production.
For above-mentioned oxidation reaction, also there is document report that potassium permanganate can be used as oxidant, but use Gao Meng
Acid potassium oxidation not only can produce the solid waste of substantial amounts of manganese containing heavy metal, and is generally also accompanied by the oxidized pair of phenyl ring
The generation of product terephthalic acid, thus pollute relatively big, it is also not suitable for industrialized production.
Content of the invention
It is an object of the invention to solve the problems referred to above, provide that a kind of yield is higher, security is higher, production cost relatively
The preparation method of 4,4 '-biphenyl dicarboxylic acid of low, applicable industrialized production.
The technical scheme realizing the object of the invention is: a kind of 4, the preparation method of 4 '-biphenyl dicarboxylic acid, it be by 4,4 '-
The oxidized reaction of diphenyl-dimethanal obtains；The oxidant that oxidation reaction uses is sodium chlorite.
Described sodium chlorite and described 4, the mol ratio of 4 '-diphenyl-dimethanal is 2: 1～4: 1, preferably 2.2: 1～2.4:
1。
Described oxidation reaction is carried out in presence of organic solvent, described organic solvent be water, methyl alcohol, ethanol or
Dichloromethane.
The temperature of described oxidation reaction is-5～10 DEG C, preferably 0～5 DEG C.
In order to eliminate the accessory substance hypochlorous acid that oxidation reaction produces, described oxidation reaction is also added with sulfamic acid or diformazan
Sulfoxide.
Described sulfamic acid or dimethyl sulfoxide and described 4, the mol ratio of 4 '-diphenyl-dimethanal is 0.5: 1～2: 1, excellent
Elect 0.9: 1～1.1 as: 1.
The good effect that the present invention has: the method reaction condition of the present invention is gentle, and security is higher, and production cost is relatively
Low, especially oxidation reaction yield is higher, good product quality, and environmental pollution is little, thus is suitable for industrialized production.
Detailed description of the invention
(embodiment 1)
By the 4 of 34.3g, the sulfamic acid of 4 '-diphenyl-dimethanal and 15.8g joins in the methyl alcohol of 250mL, controls thing under ice bath
Material temperature degree is 0～5 DEG C, and dropping 100mL contains the aqueous solution of 34.3g sodium chlorite, and about 2h drips off, and continues stirring 2h after adding,
Control in sampling HPLC, disappears to raw material, terminates reaction.
The sodium sulfite aqueous solution 30.8mL adding concentration to be 10wt%, stirs 30min, is concentrated in vacuo, removes organic molten
Agent, is then acidified to pH=1～2 with hydrochloric acid, separates out a large amount of white solid, filters, and filter cake washes with water, and vacuum drying obtains white
Look product 4,4 '-biphenyl dicarboxylic acid 37.9g, purity is 99.0%(HPLC), yield is 95.9%.
(embodiment 2～embodiment 5)
Each embodiment is substantially the same manner as Example 1, and difference is shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| 4,4 '-diphenyl-dimethanal | 34.3g | 34.3g | 34.3g | 34.3g | 34.3g |
| Sodium chlorite | 34.3g | 32.6g | 35.4g | 34.3g | 34.3g |
| Sulfamic acid | 15.8g | 15.8g | 15.8g | - | 15.8g |
| Organic solvent | 250mL methyl alcohol | 250mL ethanol | 250mL methyl alcohol | 250mL methyl alcohol | 250mL dichloromethane |
| Products weight | 37.9g | 37.7g | 37.8g | 35.9g | 37.6g |
| Purity | 99.0% | 98.8% | 98.9% | 98.1% | 98.7% |
| Yield | 95.9% | 95.4% | 95.6% | 90.8% | 94.9% |
Claims (9)
1. one kind 4, the preparation method of 4 '-biphenyl dicarboxylic acid, it is to be obtained by the oxidized reaction of 4,4 '-diphenyl-dimethanal；It is special
Levy and be: the oxidant that described oxidation reaction uses is sodium chlorite.
2. according to claim 14, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described sodium chlorite with
The mol ratio of described 4,4 '-diphenyl-dimethanal is 2: 1～4: 1.
3. according to claim 24, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described sodium chlorite with
The mol ratio of described 4,4 '-diphenyl-dimethanal is 2.2: 1～2.4: 1.
4. according to claims 1 to 34, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described oxidation reaction
Carry out in the presence of sulfamic acid or dimethyl sulfoxide.
5. according to claim 44, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described sulfamic acid or
Person's dimethyl sulfoxide is 0.5: 1～2 with the mol ratio of described 4,4 '-diphenyl-dimethanal: 1.
6. according to claim 54, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described sulfamic acid or
Person's dimethyl sulfoxide is 0.9: 1～1.1 with the mol ratio of described 4,4 '-diphenyl-dimethanal: 1.
7. according to claim 14, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described oxidation reaction is
Carry out in presence of organic solvent.
8. according to claim 74, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described organic solvent is
Water, methyl alcohol, ethanol or dichloromethane.
9. according to claim 14, the preparation method of 4 '-biphenyl dicarboxylic acid, it is characterised in that: described oxidation reaction
Temperature is 0～5 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610492195.5A CN106146286A (en) | 2016-06-29 | 2016-06-29 | The preparation method of 4,4 ' biphenyl dicarboxylic acids |
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| CN201610492195.5A CN106146286A (en) | 2016-06-29 | 2016-06-29 | The preparation method of 4,4 ' biphenyl dicarboxylic acids |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210055476A (en) | 2019-11-07 | 2021-05-17 | 조혜수 | Method of manufacturing biphenyldicarboxylic acid |
-
2016
- 2016-06-29 CN CN201610492195.5A patent/CN106146286A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 姜志猛: "亚氯酸钠体系选择性氧化制备布洛芬及其它羧酸", 《中国医药工业杂志》 * |
| 葛洪玉等: "4,4’-联苯二甲酸的合成", 《兰州理工大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210055476A (en) | 2019-11-07 | 2021-05-17 | 조혜수 | Method of manufacturing biphenyldicarboxylic acid |
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Application publication date: 20161123 |
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