CN104628556A - Preparation method of 1-(acetyl bromide)pyrene - Google Patents
Preparation method of 1-(acetyl bromide)pyrene Download PDFInfo
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- CN104628556A CN104628556A CN201510066013.3A CN201510066013A CN104628556A CN 104628556 A CN104628556 A CN 104628556A CN 201510066013 A CN201510066013 A CN 201510066013A CN 104628556 A CN104628556 A CN 104628556A
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- pyrene
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- acetobrom
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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
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
- C07C2603/50—Pyrenes; Hydrogenated pyrenes
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1-(acetyl bromide)pyrene, belonging to the field of organic chemical synthesis. The preparation method disclosed by the invention aims at solving the technical problems that the raw materials of a traditional synthesis method are expensive and the cost is high and the treatment after reaction is complicated and the product is red; according to the preparation method disclosed by the invention, a proper phase transfer catalyst is added in the reaction and a buffer solution control quenching system is added in a reaction quenching process, the expensive AlBr3 is successfully replaced by cheap anhydrous AlCl3, and the product can be obtained directly through once recrystallization after the reaction; and therefore, the preparation method disclosed by the invention has the advantages of low cost, little pollution, simple and convenient treatment after reaction, good product color and adaptability to industrial production.
Description
Technical field
The invention belongs to organic chemical synthesis field, be specifically related to a kind of 1-(acetobrom) preparation method of pyrene.
Background technology
1-(acetobrom) pyrene is a kind of important organic intermediate compound, it is the intermediate of numerous spices, dyestuff and fluorescent material.1-(acetobrom) preparation of pyrene mainly by the Bromoacetylated reaction of aromatic compound, the class namely in F-K reaction.Mainly anhydrous AlCl is used in F-K reaction
3for lewis acid catalyst, but it should be noted that the bromine atoms in the acetyl bromide in this reaction product is easily replaced by chlorine atom, and substitution product and 1-(acetobrom) pyrene character is very similar, and cause reaction conversion ratio low and be difficult to purifying.For preventing the generation of this phenomenon in reaction, this product generally adopts anhydrous AlBr
3for lewis acid catalyst is prepared.But, anhydrous AlBr
3expensive, make enterprise's production cost too high, in addition, with anhydrous AlBr
3the product colour obtained for lewis acid catalyst is rubescent, affects product look and sees, and usual needs distillation or repeatedly recrystallization are purified again, this invisible energy consumption considerably increasing this product of production.This does not meet the trend of the development of energy-saving and cost-reducing, Green Chemistry, also limit AlBr
3as the application of lewis acid catalyst.
Summary of the invention
The object of the invention is to overcome the defect that prior art exists, provide a kind of production cost low, post-reaction treatment is simple, convenient, and pollute little, product look is seen, and is applicable to the 1-(acetobrom of suitability for industrialized production) preparation method of pyrene.
For achieving the above object, the technical solution used in the present invention is: under room temperature, raw material pyrene is added successively in reaction flask, solvent and phase-transfer catalyst, reaction flask is put into cryosel bath temperature control-5 DEG C ~ 5 DEG C stirring to cause it and dissolve completely, disposablely add bromoacetyl bromide, stir, then Lewis acid and solvent is added successively, keep this temperature stirring reaction 4 ~ 6 hours, after reaction terminates, reaction solution is slowly poured in trash ice, then the pH ≈ 8 that buffered soln regulates mixture is added, separatory collects organic phase, steam except desolventizing by revolving after organic phases washed with water 2 ~ 3 times, collect solid and be 1-(acetobrom) the thick product of pyrene, thick product is through activated carbon decolorizing, filter, organic solvent recrystallization, dry, product,
Wherein, the synthetic route of described reaction is as shown in Equation 1:
(formula 1).
Being for twice same before and after described solvent, be any one in methylene dichloride, 1,2-ethylene dichloride, chloroform, and before and after solvent, the ratio of twice add-on is 3:2.
Described phase-transfer catalyst is the mixture of Tetrabutyl amonium bromide and tetraethylammonium bromide, and wherein the mixture mol ratio of Tetrabutyl amonium bromide and tetraethylammonium bromide is 1:3, and its total consumption is the 5%-10% of pyrene quality.
Described Lewis acid is Aluminum chloride anhydrous.
The mol ratio of described pyrene, bromoacetyl bromide, Aluminum chloride anhydrous and solvent total amount is 1:0.8 ~ 1.2:0.5 ~ 0.9:35 ~ 60.
The pH value of described adjustment mixture buffered soln used is the sodium hydrogen carbonate solution of massfraction 10% ~ 20%.
The organic solvent of described recrystallization is the mixed solvent of methylene dichloride and sherwood oil, and wherein, the volume ratio of methylene dichloride and sherwood oil is 2:1.
The beneficial effect that the present invention has is: the present invention controls cancellation system by the buffered soln added in the reaction in phase-transfer catalyst and reaction cancellation process, and success is with cheap anhydrous AlCl
3replace expensive AlBr
3completing this reaction, greatly reducing production cost when not affecting product yield; And post-reaction treatment of the present invention can directly by a recrystallization product, simple to operate, avoid recrystallization simultaneously and use a large amount of organic solvents, meet requirement that is energy-saving and cost-reducing, Green Chemistry; In addition, the product purity that the present invention obtains is high, and color is glassy yellow, and its look is seen and is greatly improved; The present invention is 1-(acetobrom) suitability for industrialized production of pyrene opens new method.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details, but protection scope of the present invention is not limited thereto.
Embodiment 1
Under room temperature, be equipped with in churned mechanically 5L tetra-mouthfuls of reaction flasks, add 115.4g pyrene, the methylene dichloride of 1.8L, 1.73g Tetrabutyl amonium bromide and 5.19g tetraethylammonium bromide respectively, reaction flask is put into cryosel bath temperature control-5 DEG C ~ 0 DEG C stirring and cause it and dissolve completely; Disposablely add 115g bromoacetyl bromide, the solution that stirs is brownish black; Then the methylene dichloride of 87.4g aluminum trichloride (anhydrous) and 1.2L is added successively, stir, solution colour purpling is black, and thickness gradually, keep said temperature stirring reaction 4 hours, reaction terminates reaction solution slowly to pour into cancellation in the trash ice of 10kg, then PH ≈ 8 is regulated with 10% sodium hydrogen carbonate solution, separatory collects organic phase, is spin-dried for solvent by after organic phases washed with water 2 ~ 3 times with Rotary Evaporators, collects solid and is crude product.Crude product methylene dichloride dissolves, and adds activated carbon decolorizing, filters, then with the volume ratio of methylene dichloride and sherwood oil be the mixed solvent recrystallization of 2:1 once, namely obtain glassy yellow product after drying.
Embodiment 2
Under room temperature, being equipped with in churned mechanically 5L tetra-mouthfuls of reaction flasks, adding 101.1g pyrene, 1.5L methylene dichloride, 1.44g Tetrabutyl amonium bromide and 4.33g tetraethylammonium bromide respectively, reaction flask being put into cryosel bath temperature control-5 DEG C ~ 0 DEG C stirring and causing it and dissolve completely; Disposablely add 100.1g bromoacetyl bromide, the solution that stirs is brownish black; Then the methylene dichloride of 76.1g aluminum trichloride (anhydrous) and 1 L is added successively, stir, solution colour purpling is black, and thickness gradually, keep said temperature stirring reaction 4.5 hours, reaction terminates reaction solution slowly to pour into cancellation in the trash ice of 10kg, then PH ≈ 8 is regulated with 10% sodium hydrogen carbonate solution, separatory collects organic phase, is spin-dried for solvent by after organic phases washed with water 2 ~ 3 times with Rotary Evaporators, collects solid and is crude product.Crude product methylene dichloride dissolves, and adds activated carbon decolorizing, filters, then with the volume ratio of methylene dichloride and sherwood oil be the mixed solvent recrystallization of 2:1 once, namely obtain glassy yellow product after drying.
Embodiment 3
Under room temperature, being equipped with in churned mechanically 5L tetra-mouthfuls of reaction flasks, adding 121.4g pyrene, 2.1L methylene dichloride, 1.97g Tetrabutyl amonium bromide and 5.90g tetraethylammonium bromide respectively, reaction flask being put into cryosel bath temperature control-5 DEG C ~ 0 DEG C stirring and causing it and dissolve completely; Disposablely add 121.1g bromoacetyl bromide, the solution that stirs is brownish black; Then the methylene dichloride of 76.1g aluminum trichloride (anhydrous) and 1.4 L is added successively, stir, solution colour purpling is black, and thickness gradually, keep said temperature stirring reaction 4.5 hours, reaction terminates reaction solution slowly to pour into cancellation in the trash ice of 10kg, then PH ≈ 8 is regulated with 10% sodium hydrogen carbonate solution, separatory collects organic phase, is spin-dried for solvent by after organic phases washed with water 2 ~ 3 times with Rotary Evaporators, collects solid and is crude product.Crude product methylene dichloride dissolves, and adds activated carbon decolorizing, filters, then with the volume ratio of methylene dichloride and sherwood oil be the mixed solvent recrystallization of 2:1 once, namely obtain glassy yellow product after drying.
Embodiment 4
Under room temperature, being equipped with in churned mechanically 5L tetra-mouthfuls of reaction flasks, adding 107.1g pyrene, 1.8L methylene dichloride, 1.47g Tetrabutyl amonium bromide and 4.42g tetraethylammonium bromide respectively, reaction flask being put into cryosel bath temperature control-5 DEG C ~ 0 DEG C stirring and causing it and dissolve completely; Disposablely add 106.9g bromoacetyl bromide, the solution that stirs is brownish black; Then the methylene dichloride of 77.8g aluminum trichloride (anhydrous) and 1.2 L is added successively, stir, solution colour purpling is black, and thickness gradually, keep said temperature stirring reaction 5 hours, reaction terminates reaction solution slowly to pour into cancellation in the trash ice of 10kg, then PH ≈ 8 is regulated with 10% sodium hydrogen carbonate solution, separatory collects organic phase, is spin-dried for solvent by after organic phases washed with water 2 ~ 3 times with Rotary Evaporators, collects solid and is crude product.Crude product methylene dichloride dissolves, and adds activated carbon decolorizing, filters, then with the volume ratio of methylene dichloride and sherwood oil be the mixed solvent recrystallization of 2:1 once, namely obtain glassy yellow product after drying.
Claims (8)
1. 1-(acetobrom) preparation method of pyrene, it is characterized in that: it is realized by following steps:
Under room temperature, raw material pyrene is added successively in reaction flask, solvent and phase-transfer catalyst, reaction flask is put into cryosel bath temperature control-5 DEG C ~ 5 DEG C stirring to cause it and dissolve completely, disposablely add bromoacetyl bromide, stir, then Lewis acid and solvent is added successively, keep this temperature stirring reaction 4 ~ 6 hours, after reaction terminates, reaction solution is slowly poured in trash ice, then the pH ≈ 8 that buffered soln regulates mixture is added, separatory collects organic phase, steam except desolventizing by revolving after organic phases washed with water 2 ~ 3 times, collect solid and be 1-(acetobrom) the thick product of pyrene, thick product is through activated carbon decolorizing, filter, organic solvent recrystallization, dry, product,
Wherein, the synthetic route of described reaction is as shown in Equation 1:
(formula 1).
2. a kind of 1-(acetobrom as claimed in claim 1) preparation method of pyrene, it is characterized in that: before and after described solvent, twice is same, is any one in methylene dichloride, 1,2-ethylene dichloride, chloroform.
3. a kind of 1-(acetobrom as described in any one of claim 1 or 2) preparation method of pyrene, it is characterized in that: before and after described solvent, the ratio of twice add-on is 3:2.
4. a kind of 1-(acetobrom as claimed in claim 1) preparation method of pyrene, it is characterized in that: described phase-transfer catalyst is the mixture of Tetrabutyl amonium bromide and tetraethylammonium bromide, wherein Tetrabutyl amonium bromide and the mixture quality of tetraethylammonium bromide are than being 1:3, and its total consumption is the 5%-10% of pyrene quality.
5. a kind of 1-(acetobrom as claimed in claim 1) preparation method of pyrene, it is characterized in that: described Lewis acid is Aluminum chloride anhydrous.
6. a kind of 1-(acetobrom as claimed in claim 1) preparation method of pyrene, it is characterized in that: the mol ratio of described pyrene, bromoacetyl bromide, Aluminum chloride anhydrous and solvent total amount is 1:0.8 ~ 1.2:0.5 ~ 1.2:35 ~ 60.
7. a kind of 1-(acetobrom as claimed in claim 1) preparation method of pyrene, it is characterized in that: the pH value of described adjustment mixture buffered soln used is the sodium hydrogen carbonate solution of massfraction 10% ~ 20%.
8. a kind of 1-(acetobrom as claimed in claim 1) preparation method of pyrene, it is characterized in that: the organic solvent of described recrystallization is the mixed solvent of methylene dichloride and sherwood oil, wherein, the volume ratio of methylene dichloride and sherwood oil is 2:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114214410A (en) * | 2021-12-24 | 2022-03-22 | 武汉承启医学检验实验室有限公司 | Method for detecting cfDNA methylation degree of blood |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61176537A (en) * | 1985-02-01 | 1986-08-08 | Mitsubishi Chem Ind Ltd | Acylation of aromatic compound |
| JPH0377845A (en) * | 1989-08-18 | 1991-04-03 | Agency Of Ind Science & Technol | Production of acylated naphthalenes |
| US5296636A (en) * | 1992-01-30 | 1994-03-22 | Basf Aktiengesellschaft | Preparation of 2,4,6-trimethylbenzoic acid |
| CN101863832A (en) * | 2010-06-13 | 2010-10-20 | 湖北远成药业有限公司 | Method for producing miconazole nitrate on industrialized basis |
-
2015
- 2015-02-09 CN CN201510066013.3A patent/CN104628556A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61176537A (en) * | 1985-02-01 | 1986-08-08 | Mitsubishi Chem Ind Ltd | Acylation of aromatic compound |
| JPH0377845A (en) * | 1989-08-18 | 1991-04-03 | Agency Of Ind Science & Technol | Production of acylated naphthalenes |
| US5296636A (en) * | 1992-01-30 | 1994-03-22 | Basf Aktiengesellschaft | Preparation of 2,4,6-trimethylbenzoic acid |
| CN101863832A (en) * | 2010-06-13 | 2010-10-20 | 湖北远成药业有限公司 | Method for producing miconazole nitrate on industrialized basis |
Non-Patent Citations (2)
| Title |
|---|
| HANNA PALONIEMI等: "Water-Soluble Full-Length Single-Wall Carbon Nanotube Polyelectrolytes: Preparation and Characterization", 《THE JOURNAL OF PHYSICAL CHEMISTRY B》 * |
| SPIJKER, NYNKE M等: "A very convenient synthesis of cyclopenta[cd]pyrene", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114214410A (en) * | 2021-12-24 | 2022-03-22 | 武汉承启医学检验实验室有限公司 | Method for detecting cfDNA methylation degree of blood |
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Application publication date: 20150520 |