CN102850251A - Dipyrromethene compound synthetic method - Google Patents
Dipyrromethene compound synthetic method Download PDFInfo
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- CN102850251A CN102850251A CN2011101742344A CN201110174234A CN102850251A CN 102850251 A CN102850251 A CN 102850251A CN 2011101742344 A CN2011101742344 A CN 2011101742344A CN 201110174234 A CN201110174234 A CN 201110174234A CN 102850251 A CN102850251 A CN 102850251A
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- dipyrrylmethanes
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Abstract
A dipyrromethene compound green synthetic method, especially a synthetic method for pyrrolo Beta-position non-substituted dipyrromethane using pyrrole and aromatic aldehydes and ketones, includes using water as solvent, using pyrrole and aromatic aldehydes and ketones as raw material and phosphotungstic acid as catalyst, and synthesizing dipyrromethane at room temperature in one-step. The dipyrromethane has yield of 44%-95% and purity greater than 99%, and the inventive method avoids the use of organic solvent of greater toxicity and the yield increased by 14%-28%, and it significantly reduces the cost and is batch synthesis process.
Description
Technical field
The present invention relates to a kind of synthetic method of dipyrrylmethanes compounds, especially a kind of take pyrroles and aromatic aldehyde as raw material the method for synthetic dipyrrylmethanes compounds.
Background technology
Dipyrrylmethanes of many uses, both can with metal complex after be used for CO as the efficient redox catalyst of a class
2Reduction, the oxidation of hydro carbons; Can be used as again and synthesize the porphyrin superpolymer with special light electrical properties such as liquid crystal
1-5Precursor; Simultaneously can also be as the photochemical treatment medicine of porphyrin of synthetic some particular space structure
6-8Precursor.But the universal method that does not also have a kind of efficient synthetic dipyrrylmethanes at present, the synthetic main following methods that adopts of the dipyrrylmethanes that at present laboratory study is used:
Above-mentioned synthetic method is different according to the kind of organic solvent, and its used acid is not identical yet.Organic solvent is mainly the large organic solvents of toxicity such as methylene dichloride, trichloromethane, DMF, acetonitrile.Catalyzer is trifluoroacetic acid, etherate of trifluoroboron, SnCl
3Etc. the more expensive organic acid catalyst of the larger price of toxicity.Reaction conditions mostly is anhydrous and oxygen-free, and condition is harsh, and operational difficulty, the productive rate of target product are 30%～67%, and last handling process is complicated, relies on loaded down with trivial details column chromatography, is difficult to realize the synthetic of economy, batch.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, take the lead in providing that a kind of yield is high, production cost is low, the green synthesis method of the dipyrrylmethanes compounds that process is easy.
The structural formula of dipyrrylmethanes compounds provided by the invention is as follows:
R1, R2 are H, alkyl, phenyl or substituted-phenyl.
The object of the present invention is achieved like this: under the normal temperature, and take deionized water as solvent, phospho-wolframic acid or HCl (36%, wt) be catalyzer, the pyrroles of pyrroles or beta substitution and fragrant aldehydes or ketones are raw material, the one-step synthesis dipyrrylmethanes.
The synthetic route of the present invention's dipyrrylmethanes compounds is as follows:
Step and the condition of method of the present invention are as follows: add deionized water in three mouthfuls of reactors with Dropping feeder, the mol ratio by 1: 2～6 drops into the pyrroles of carbonyl compound and pyrroles or beta substitution, and the concentration of the carbonyl compound in the reaction system is 2 * 10
-3～1.4mol/L, nitrogen purging solution is to remove the oxygen in anhydrating; And then input phosphate-tungstic acid, after with system sealing, the mol ratio of phosphate-tungstic acid and carbonyl compound is 0.1-05: 1, react under the nitrogen protection, 25 ℃ of temperature of reaction, stir, react after 12-72 hour, add proper ammonia and make solution PH cancellation reaction between 6-7, suction filtration, the filter cake distilled water wash, vacuum-drying obtains the dipyrrylmethanes compounds; Described carbonyl compound is phenyl aldehyde, p-Hydroxybenzaldehyde, paranitrobenzaldehyde, methyl phenyl ketone or aubepine.
Beneficial effect: method of the present invention, the solvent that uses in the building-up process and catalyzer are all nontoxic, also do not produce any three wastes big for environment pollution, and green degree is high, and product postprocessing is simple, and is with low cost, is fit to suitability for industrialized production.The method productive rate of extensive synthetic dipyrrylmethanes compounds can reach 44%～95%, and 14%-28% improves greatly than the bibliographical information value, is the friendly process that is applicable in batches synthetic dipyrrylmethanes compounds.
Embodiment
Embodiment 1 is to adding the 50mL deionized water in the there-necked flask of Dropping feeder, the phenyl aldehyde of 0.5mL (5mmol) and 2mL (30mmol) pyrroles, and the concentration of the phenyl aldehyde in the reaction system is 2 * 10
-3～1.4mol/L; Nitrogen purging solution 10min is to remove the oxygen in anhydrating; After adding 1.4g (0.15mmol) phospho-wolframic acid system is sealed; nitrogen protection; 25 ℃ of temperature of reaction stir, and react 12 hours; adding proper ammonia makes solution PH react in 6.5 cancellation; suction filtration, filter cake distilled water wash 5 times, 40 ℃ of vacuum-dryings; obtain 5-phenyl dipyrrylmethanes 0.91g, productive rate 82%.
The structural characterization data of product: mp=100 ℃,
1H NMR (400MHz, CDCl
3): δ 5.45 (br s, 1H, mesoH), 5.90 (m, 2H, 2C
3-H), 6.14 (dd, 2H, J=2.8,5.8,2C
4-H), 6.67 (br d, 2H, J=2.8,2C
5-H), 7.20 (m, 2H, H-Ar), 7.25 (m, 2H, Ar-H), 7.88 (br s, 2H, N-H).
Table one
Embodiment 2 processing condition see Table shown in one, and remaining obtains 5-(4-hydroxy phenyl) dipyrrylmethanes 0.65g, productive rate 55% with embodiment 1.
The structural characterization data of product: mp=158 ℃.
1HNMR(400MHz，CDCl
3)：δ5.40(s，1H，mesoH)，5.90(m，2H，2C
3-H)，6.14(dd，2H，J＝2.8，5.8，2C
4-H)，6.67(m，2H，2C
5-H)，6.75(d，2H，J＝8.5，H-Ar)，7.05(d，2H，J＝8.5，Ar-H)，7.96(br?s，2H，N-H).
Embodiment 3 processing condition see Table shown in one, and remaining obtains 5-(4-nitrophenyl) dipyrrylmethanes 1.3g, yield 95% with embodiment 1.
Characterization data: mp=159 ℃.
1H?NMR(400MHz，CDCl
3)：δ5.58(s，1H，mesoH)，5.87(d，2H，J＝5.7Hz，2C
3-H)，6.17(dd，2H，J＝2.8，5.7，2C
4-H)，6.74(dd，2H，J＝2.8，1.2，2C
5-H)，7.36(d，2H，J＝8.6，H-Ar)，7.98(br?s，2H，N-H)，8.16(d，2H，J＝8.6，Ar-H).
Embodiment 4 processing condition see Table shown in one, and remaining obtains 5-methyl-5-phenyl dipyrrylmethanes 0.50g with embodiment 1.Yield 45%.
Characterization data: mp=127-129 ℃.
1H?NMR(400MHz，CDCl
3)：δ2.33(s，3H)，5.43(s，1H)，5.91(s，2H)，6.15(d，2H，J＝2.7HZ)，6.68(d，2H，J＝1.1HZ)，7.09-7.25(m，?4H，Ar-H)，7.93(s，2H，N-H).
Embodiment 5 processing condition see Table shown in one, and remaining obtains 5-(4-p-methoxy-phenyl) dipyrrylmethanes 1.1g, yield 90% with embodiment 1.
Characterization data: mp=99 ℃.
1H?NMR(400MHz，CDCl
3)：δ3.78(s，3H，CH
3)，5.40(s，1H，mesoH)，5.90(m，2H，2C
3-H)，6.14(dd，2H，J＝2.8，5.9，2C
4-H)，6.67(m，2H，2C
5-H)，6.84(d，2H，J＝8.7，H-Ar)，7.12(d，2H，J＝8.7，Ar-H)，7.92(br?s，2H，N-H)。
Claims (3)
1. the synthetic method of a dipyrrylmethanes, it is characterized in that step and condition are as follows: in three mouthfuls of reactors with Dropping feeder, add deionized water, mol ratio by 1: 2～6 drops into the pyrroles of carbonyl compound and pyrroles or beta substitution, and the concentration of the carbonyl compound in the reaction system is 2 * 10
-3～1.4mol/L, nitrogen purging solution is to remove the oxygen in anhydrating; And then input phosphate-tungstic acid, after with system sealing, the mol ratio of phosphate-tungstic acid and carbonyl compound is 0.1-05: 1, react under the nitrogen protection, 25 ℃ of temperature of reaction, stir, react after 12-72 hour, add proper ammonia and make solution PH cancellation reaction between 6-7, suction filtration, the filter cake distilled water wash, vacuum-drying obtains the dipyrrylmethanes compounds; Described carbonyl compound is phenyl aldehyde, p-Hydroxybenzaldehyde, paranitrobenzaldehyde, methyl phenyl ketone or aubepine.
2. the synthetic method of a kind of dipyrrylmethanes as claimed in claim 1, it is characterized in that step and condition are as follows: in the there-necked flask with Dropping feeder, add deionized water, the phenyl aldehyde of 5mmol and 30mmol pyrroles, the concentration of the phenyl aldehyde in the reaction system is 2 * 10
-3～1.4mol/L; Nitrogen purging solution 10min is to remove the oxygen in anhydrating; After adding the 0.15mmol phospho-wolframic acid system is sealed, nitrogen protection, 25 ℃ of temperature of reaction stir; reacted 12 hours, and added proper ammonia and make solution PH react suction filtration in 6.5 cancellation; the filter cake distilled water wash, 40 ℃ of vacuum-dryings obtain 5-phenyl dipyrrylmethanes.
3. the synthetic method of a kind of dipyrrylmethanes as claimed in claim 1 is characterized in that
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201647A (en) * | 2019-05-31 | 2019-09-06 | 西安交通大学 | A kind of two (polyalcohol methane) adsorbent of poly- pyrroles -2,5- and preparation method |
-
2011
- 2011-06-27 CN CN2011101742344A patent/CN102850251A/en active Pending
Non-Patent Citations (5)
| Title |
|---|
| ABILIO J. F. N. SOBRAL ET AL.: "One-step synthesis of dipyrromethanes in water", 《TETRAHEDRON LETTERS》 * |
| TAOUFIK ROHAND ET AL.: "Efficient synthesis of aryldipyrromethanes in water and their application in the synthesis of corroles and dipyrromethenes", 《ARKIVOC》 * |
| ZHANG YAN ET AL.: "Fast and Eco-friendly Synthesis of Dipyrromethanes by H2SO4•SiO2 Catalysis under Solvent-free Conditions", 《CHIN. J. CHEM.》 * |
| ZHANG YAN ET AL.: "Fast and Eco-friendly Synthesis of Dipyrromethanes by H2SO4•SiO2 Catalysis under Solvent-free Conditions", 《CHIN. J. CHEM.》, vol. 28, 31 December 2010 (2010-12-31), pages 259 - 262 * |
| 邢烨: "杂多酸催化有机反应的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201647A (en) * | 2019-05-31 | 2019-09-06 | 西安交通大学 | A kind of two (polyalcohol methane) adsorbent of poly- pyrroles -2,5- and preparation method |
| CN110201647B (en) * | 2019-05-31 | 2020-08-18 | 西安交通大学 | Poly-pyrrole-2, 5-di (polyalcohol methane) adsorbent and preparation method thereof |
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