CN102952141A - Synthesis method of meso-tetra[4-(3,4-dimethoxybenzyloxy)phenyl]porphyrin - Google Patents
Synthesis method of meso-tetra[4-(3,4-dimethoxybenzyloxy)phenyl]porphyrin Download PDFInfo
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- CN102952141A CN102952141A CN2011102517199A CN201110251719A CN102952141A CN 102952141 A CN102952141 A CN 102952141A CN 2011102517199 A CN2011102517199 A CN 2011102517199A CN 201110251719 A CN201110251719 A CN 201110251719A CN 102952141 A CN102952141 A CN 102952141A
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Abstract
The invention discloses a synthesis method of a novel porphyrin compound, namely meso-tetra[4-(3,4-dimethoxybenzyloxy)phenyl]porphyrin. The meso-tetra[4-(3,4-dimethoxybenzyloxy)phenyl]porphyrin is synthesized from propanoic acid, glacial acetic acid and nitrobenzene through a mixed-solvent method. The invention also discloses a synthesis process of 4-(3,4-dimethoxybenzyloxy)benzaldehyde, which is simple to operate, easy to perform post treatment, very high in yield and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of new porphyrin compound is the synthetic method of meso-four [4-(3,4-dimethoxy benzyloxy) phenyl] porphyrin, also discloses simultaneously the synthetic method of 4-(3,4-dimethoxy benzyloxy) phenyl aldehyde.
Background technology
Porphyrin compound is a kind of special macrocylc compound, with the biological phenomena close relation, extensively is present in the animals and plants, has special physiologically active, as: protoheme, chlorophyll, cytochrome P-450 etc.Because its unique structure and distinctive performance, have very widely purposes in fields such as electrochemistry, photochemistry, analytical chemistry and bionic catalysis, their research is more and more come into one's own.
The porphyrin compound that contains alkoxy grp has very important purposes at analytical chemistry, be widely used in surveying Pb, the trace metal ions such as Hg, the porphyrin compound that contains benzyloxy involved in the present invention are a kind of new porphyrins, and foreign literature only has the similar porphyrin of Lindesy method stepwise synthesis, need for a long time, the present invention replaces propionic acid single-solvent process commonly used synthetic with mixed solvent method, effectively reduces the generation of by product, Reaction time shorten, make purification easier, productive rate also increases.
The 4-that the present invention synthesized (3,4-dimethoxy benzyloxy) phenyl aldehyde is a kind of novel compound, by 3, the 4-dimethoxy benzaldehyde becomes three steps of ether synthetic through reduction, chlorination and Williamson, per step purity and productive rate are all very high, easy and simple to handle, are fit to industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic mixed solvent method that contains the porphyrin compound of benzyloxy, be specially meso-four [4-(3,4-dimethoxy benzyloxy) phenyl] porphyrin, the method can effectively reduce the generation of by product, Reaction time shorten, the productive rate of raising porphyrin.4-(3, the 4-dimethoxy benzyloxy) synthetic method of phenyl aldehyde also is provided simultaneously, has specifically comprised the reduction of aldehyde, the chlorination of alcohol, Williamson method ether synthetic, per step is all easy and simple to handle, purity and productive rate are very high, more can be generalized to other and contain the synthetic of benzyloxy aromatic aldehyde.
To achieve these goals, technical scheme provided by the invention is: synthesize first 4-(3,4-dimethoxy benzyloxy) phenyl aldehyde, again with synthetic meso-four [4-(3, the 4-dimethoxy benzyloxy) phenyl] porphyrin of mixed solvent method.
Concrete synthetic route is as follows:
Synthetic schemes may further comprise the steps:
(1) veratryl aldehyde 1eq is dissolved in the methyl alcohol, and ice-water bath is cooled to 0 ℃, adds sodium borohydride 1.95eq, and the control temperature adds rear continuation reaction 30min at 0-5 ℃, drips the water termination reaction.Reaction mixture is poured into water, and the ethyl acetate extraction several times are spin-dried for and namely get veratryl alcohol (1).
(2) veratryl alcohol 1eq is dissolved in the methylene dichloride, and ice-water bath is cooled to 0 ℃, drips pyridine 1eq behind the dropping sulfur oxychloride 2eq, and reaction adds the entry termination reaction after finishing, and the dichloromethane extraction several times are spin-dried for and namely get 3,4-dimethoxy benzyl chlorine (2).
(3) p-Hydroxybenzaldehyde 1eq and K
2CO
3Be dissolved in first DMF and form suspension, stir 15min, then drip 3,4-dimethoxy benzyl chlorine 1.3eq is dissolved in the solution of DMF, reacts 6-8h under the room temperature, directly pours in the mixture of ice and water after the end, the suction filtration oven dry namely gets 4-(3,4-dimethoxy benzyloxy) phenyl aldehyde (3).
(4) get propionic acid, oil of mirbane and Glacial acetic acid and add there-necked flask, be heated with stirring to backflow, drip 4-(3 in the 10min, 4-dimethoxy benzyloxy) phenyl aldehyde 1eq is dissolved in the solution of propionic acid, then drip the solution that 1eq pyrroles is dissolved in Glacial acetic acid in 10min, reflux 40min gets atropurpureus solution.Direct nearly half solvent of pressure reducing and steaming after the solution cooling, add equivalent methyl alcohol in the residue mother liquor, refrigerator cold-storage spends the night, suction filtration gets green solid, and methyl alcohol, water washing are colourless to filtrate, and methylene dichloride is eluent, silica gel column chromatography, collect red-purple the first colour band, vacuum-drying gets meso-four [4-(3,4-dimethoxy benzyloxy) phenyl] porphyrin (4).
The method that contains the benzyloxy aromatic aldehyde of synthesizing disclosed in this invention is easy and simple to handle, and productive rate is very high, and purity is good, can be generalized to the synthetic of other aromatic aldehydes, has ubiquity.
The present invention is a kind of new porphyrin with the synthetic porphyrin compound that contains benzyloxy of mixed solvent method, crude product is green, differ from general porphyrin compound, be common purple after purifying, mixed solvent replaces the propionic acid single solvent can effectively reduce by product, simplify and purify, equally also can be generalized to the synthetic of other porphyrin compounds.
Embodiment
Below in conjunction with specific embodiment the technical scheme of invention is done step explanation:
Embodiment 1
With 3,4-dimethoxy benzaldehyde (veratryl aldehyde) 10g (61.5mmol) is dissolved in 100ml methyl alcohol, ice-water bath is cooled to 0 ℃, take by weighing sodium borohydride 4.55g (120mmol) slowly adds wherein in batches, the control temperature is at 0-5 ℃, continue stirring reaction 30min, slowly drip 100ml water termination reaction, then reaction mixture is poured in the 100ml water, with ethyl acetate extraction 3 times, merge organic phase, anhydrous sodium sulfate drying, decompression steams solvent, namely gets colourless oil liquid veratryl alcohol (1) 9.75g (yield is 95%).
Embodiment 2
Veratryl alcohol 8.75g (52mmol) is dissolved in the 200ml methylene dichloride, ice-water bath is cooled to 0 ℃, slowly drip sulfur oxychloride 12.4g (104mmol), then drip pyridine 4.11g (53mmol), continue stirring reaction 1h, TLC follows the tracks of reaction to finishing, drip 200ml water termination reaction, organic phase is separated, residue water dichloromethane extraction, merge organic phase, anhydrous sodium sulfate drying removes solvent under reduced pressure, namely gets colourless liquid, cooling curing becomes white solid 3,4-dimethoxy benzyl chlorine (2) 9.18g (yield is 95%).
Embodiment 3
P-Hydroxybenzaldehyde 3.78g (31mmol) and salt of wormwood 8.5g are put into there-necked flask, add N, dinethylformamide (DMF) 25ml, stir 15min and form suspension, drip 3,4-dimethoxy benzyl chlorine 7.47g (40mmol) is dissolved in the solution of 10mlDMF, react 6-8h under the room temperature, TLC follows the tracks of reaction to finishing, pour into and separate out immediately a large amount of solids in the mixture of ice and water, suction filtration washes several times with water, be drying to obtain white solid 4-(3,4-dimethoxy benzyloxy) phenyl aldehyde (3) 7.6g (yield is 90%).
Embodiment 4
Get 20ml propionic acid, 20ml oil of mirbane and 30ml Glacial acetic acid and add the 250ml there-necked flask, mechanical stirring, be heated to 128 ℃ of backflows, drip 4-(3 in the 10min, 4-dimethoxy benzyloxy) phenyl aldehyde 5.45g (20mmol) is dissolved in the solution of 20ml propionic acid, then drip the solution that 1.4ml pyrroles (20mmol) is dissolved in the 20ml Glacial acetic acid in 10min, reflux 40min gets atropurpureus solution.Direct nearly half solvent of pressure reducing and steaming after the solution cooling, add equivalent methyl alcohol in the residue mother liquor, refrigerator cold-storage spends the night, suction filtration gets green solid, and (this porphyrin crude product color and other are not quite alike, crude product is green, heat is with regard to purple a little), methyl alcohol, water washing are colourless to filtrate, methylene dichloride is eluent, silica gel column chromatography, collect red-purple the first colour band, vacuum-drying gets brilliant violet look crystal meso-four [4-(3,4-dimethoxy benzyloxy) phenyl] porphyrin (4) 1.16g (yield is 18%).
Claims (4)
1. synthetic method that contains the Novel Porphyrin of benzyloxy, it is characterized in that: the porphyrin that is synthesized is meso-four [4-(3,4-dimethoxy benzyloxy) phenyl] porphyrin, and its structural formula is as follows:
2. method according to claim 1 is characterized in that: synthetic used 4-(3, the 4-dimethoxy benzyloxy) phenyl aldehyde of this porphyrin is a kind of novel compound, and its synthesis step is as follows:
(1) Veratraldehyde (veratryl aldehyde) is dissolved in the methyl alcohol, and ice-water bath is cooled to 0 ℃, then slowly adds sodium borohydride in batches, and the control temperature adds rear continuation reaction 30min at 0-5 ℃, drips the water termination reaction.Reaction mixture is poured into water, and the ethyl acetate extraction several times merge organic phase, anhydrous Na
2SO
4Drying is spin-dried for and namely gets 3,4-dimethoxy-benzene methyl alcohol (veratryl alcohol).
(2) veratryl alcohol is dissolved in the methylene dichloride, and ice-water bath is cooled to 0 ℃, drips pyridine behind the dropping sulfur oxychloride, and TLC follows the tracks of reaction and finishes, and then adds the entry termination reaction, and the dichloromethane extraction several times merge organic phase, anhydrous Na
2SO
4Drying is spin-dried for and namely gets 3,4-dimethoxy benzyl chlorine.
(3) p-Hydroxybenzaldehyde and K
2CO
3Be dissolved in first DMF and form suspension, stir 15min, then drip 3,4-dimethoxy benzyl chlorine is dissolved in the solution of DMF, reacts 6-8h under the room temperature, directly pours in the mixture of ice and water after the end, separate out a large amount of solids, the suction filtration oven dry namely gets 4-(3,4-dimethoxy benzyloxy) phenyl aldehyde.
3. method according to claim 5 is characterized in that: the sodium borohydride consumption is with respect to veratryl aldehyde excessive nearly one times in the step 1, adds the water termination reaction and gets final product; The adding of pyridine can improve productive rate in the step 2, and the sulfur oxychloride consumption is 2 times of veratryl alcohol; In the step 33,4-dimethoxy benzyl chlorine is solid after solidifying, and drips after being dissolved in DMF.
4. method according to claim 1, it is characterized in that: with synthetic this porphyrin of mixed solvent method, be propionic acid, Glacial acetic acid and oil of mirbane in 2: 2: 1-2: after 3: 1 ratio Hybrid Heating reflux, drip first 4-(3,4-dimethoxy benzyloxy) phenyl aldehyde is dissolved in the solution of propionic acid, drips the solution that the pyrroles is dissolved in Glacial acetic acid again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110251719.9A CN102952141B (en) | 2011-08-30 | The synthetic method of meso-tetra-[4-(3,4-dimethoxybenzyloxycarbonyl base) phenyl] porphyrin |
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| CN201110251719.9A CN102952141B (en) | 2011-08-30 | The synthetic method of meso-tetra-[4-(3,4-dimethoxybenzyloxycarbonyl base) phenyl] porphyrin |
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| CN102952141A true CN102952141A (en) | 2013-03-06 |
| CN102952141B CN102952141B (en) | 2016-12-14 |
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| CN104139740A (en) * | 2013-05-07 | 2014-11-12 | 大陆汽车投资（上海）有限公司 | Movable in-vehicle display equipment and vehicle-mounted multimedia system |
| CN105906637A (en) * | 2016-05-16 | 2016-08-31 | 广东工业大学 | Preparation method of Meso-tetra(3,4-dimethoxy phenyl) porphyrin cobalt |
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| CN101258119A (en) * | 2005-07-25 | 2008-09-03 | 恩多拉公司 | Process for preparing 3,4-dioxo-substituted aromatic aldehydes |
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| CN101258119A (en) * | 2005-07-25 | 2008-09-03 | 恩多拉公司 | Process for preparing 3,4-dioxo-substituted aromatic aldehydes |
| WO2007081490A1 (en) * | 2006-01-04 | 2007-07-19 | Kent State University | Light-harvesting discotic liquid crystalline porphyrins and metal complexes |
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| XUEFEN TAO等: "Synthesis and antitumor activity of 2-aryl-1,2,4-triazolo[1,5-a] pyridine derivatives", 《MEDICINAL CHEMISTRY》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104139740A (en) * | 2013-05-07 | 2014-11-12 | 大陆汽车投资（上海）有限公司 | Movable in-vehicle display equipment and vehicle-mounted multimedia system |
| CN105906637A (en) * | 2016-05-16 | 2016-08-31 | 广东工业大学 | Preparation method of Meso-tetra(3,4-dimethoxy phenyl) porphyrin cobalt |
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Granted publication date: 20161214 Termination date: 20170830 |