CN101665494A - Tailed tetrasulfhydryl porphyrin with carbon chain length of 6 - Google Patents
Tailed tetrasulfhydryl porphyrin with carbon chain length of 6 Download PDFInfo
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- CN101665494A CN101665494A CN200810150905A CN200810150905A CN101665494A CN 101665494 A CN101665494 A CN 101665494A CN 200810150905 A CN200810150905 A CN 200810150905A CN 200810150905 A CN200810150905 A CN 200810150905A CN 101665494 A CN101665494 A CN 101665494A
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- porphyrin
- tetrasulfhydryl
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Abstract
The invention relates to tailed tetrasulfhydryl porphyrin with the carbon chain length of 6, which has a structural formula shown on the right. A preparation method comprises the steps of starting from tetrahydroxyl porphyrin and performing bromination, esterification and hydrolysis in turn to prepare the tailed tetrasulfhydryl porphyrin with the carbon chain length of 6. The tetrasulfhydryl porphyrin synthesized in the invention is of certain practical value to the aspects of study on electron transfer, molecular catalysis, photoinduced molecular switches, molecular rectifiers and layer-by-layer assembly.
Description
Technical field
The present invention relates to porphyrins, be meant that especially a kind of carbon chain lengths is 6 tail formula four sulfydryl porphyrins.
Background technology
Porphyrin is a kind of basic biomolecules that nature extensively exists, and many biomolecules such as oxyphorase, myohaemoglobin, the isostructural core of cytopigment all are porphyrinses.Porphyrins is because of the two dimensional structure of its molecule and easy characteristics such as modification property, is widely used in research fields such as analytical chemistry, bionical, catalysis, medical science and Materials science.Long-range transfer transport mechanism between out-phase is significant in chemistry and bioprocess, is the basic steps of many vital movements.Because sulphur atom is easy and gold surface forms firm covalent linkage (S-Au), sulfydryl (SH) usually is introduced into the porphyrin molecule, forms high-sequential, thermodynamically stable porphyrin self-assembled monolayer.Therefore transfer transport the most basic in the life entity can be simulated in the interface that the sulfydryl porphyrin is constructed by self-assembling technique, thereby reach screening optimal drug molecule, purposes such as control electron transfer process.
Summary of the invention
The object of the present invention is to provide a kind of carbon chain lengths is 6 four sulfydryl porphyrin compounds.Its preparation method is to be set out by the tetrahydroxy porphyrin, successively by bromination, and esterification, hydrolytic process obtains four sulfydryl porphyrins.
The objective of the invention is to be achieved through the following technical solutions:
A kind of carbon chain lengths is 6 four sulfydryl porphyrin compounds, and structural formula is as follows:
The preparation carbon chain lengths is that the method for 6 four sulfydryl porphyrin compounds is finished by following steps:
(a) the 4-hydroxy benzaldehyde is joined in the propionic acid solution, fully stir, progressively splash into new steaming pyrroles, its mol ratio is 1: 1, and 130～140 ℃ of backflows were reacted 40 minutes, when being cooled to 60 ℃, add dehydrated alcohol again, stir and be cooled to room temperature, uncovered standing over night, suction filtration, colourless with the propionic acid washing leaching cake to filtrate. after the vacuum-drying, obtain thick product, thick product silica gel column chromatography is separated, promptly get 5,10,15,20-four (4-hydroxy phenyl) porphyrin;
Its reaction formula is as follows:
(b) with 5,10,15,20-four (4-hydroxy phenyl) porphyrin and salt of wormwood room temperature are dissolved in N, in the dinethylformamide (DMF), stir, and slowly drip 1,6-dibromo-hexane, wherein 5,10,15, the mol ratio of 20-four (4-hydroxy phenyl) porphyrin and dibromo-hexane reagent is 1: 40, after 20～25 ℃ of reactions, use dichloromethane extraction, merge organic layer, anhydrous magnesium sulfate lucifuge drying. silica gel column chromatography separates, and promptly gets corresponding brominated product;
Reaction formula is as follows:
(c) above-mentioned (b) gained brominated product is dissolved in organic solvent CHCl
3In, add Anhydrous potassium carbonate and thioacetic acid, in 80 ℃ of oil baths, refluxed 3 hours under the nitrogen protection, postcooling to 20～25 ℃, saturated common salt water washing organic phase are to neutral, dichloromethane extraction, merge organic layer, anhydrous magnesium sulfate lucifuge drying, silica gel column chromatography separates, and promptly gets corresponding sulfo-esterification products;
Reaction formula is as follows:
(d) above-mentioned (c) sulfo-esterification products is dissolved in the mixed solvent of chloroform and methyl alcohol N in KOH solution
2Protect, 80～90 ℃ of backflows,, chloroform extraction, saturated common salt water washing organic phase is to neutral, and anhydrous magnesium sulfate seals the lucifuge drying, and silica gel column chromatography separates, and the sherwood oil recrystallization gets the sulfydryl substitution product, and KOH solution is to be dissolved in 3mL CH by 1.0g KOH
3OH and 2mL H
2O is formulated;
Reaction formula is as follows:
Advantage of the present invention:
1, the present invention adopts the combination of Adler method and Lindsey method, has prepared a kind of carbon chain lengths and be 6 tailed sulfhydryl porphyrin.The diversity of porphyrin molecular structure and easily cutting provide the possibility of synthesizing various derivatives of porphyrin to people.Because sulphur atom is easy and gold surface forms firm covalent linkage (S-Au), so sulfydryl (SH) usually is introduced into the porphyrin molecule, forms high-sequential, thermodynamically stable porphyrin self-assembled monolayer.Four sulfydryl porphyrins with respect to single sulfydryl porphyrin can better with the gold surface combination, and in conjunction with after exposed sulfydryl is arranged, thereby can combine with other material the realization layer assembly.Therefore institute of the present invention synthetic four sulfydryl porphyrins are to realizing transfer transport research and Journal of Molecular Catalysis and photic molecular switch, and there is certain practical value molecular rectifier and layer assembly aspect.
2, during synthetic the first step tetrahydroxy porphyrin, temperature of reaction is controlled between 130 ℃ to 140 ℃, and the pyrroles is added drop-wise in the propionic acid solution with very slow speed, fully stirs, and has prevented reactant pyrroles's polymerization.
Embodiment:
14.34g (0.1175mol) 4-hydroxy benzaldehyde is joined in 100 ℃ of little propionic acid solution that boil of 200mL, mechanical stirring, slowly splash into new steaming pyrroles 4.0ml (0.1175mol) with 0.5 droplet/second speed then, dripping off in 30 minutes. reaction solution continued to be heated to 140 ℃ of backflows after 1 hour, stirring is cooled to 60 ℃, add the 100mL dehydrated alcohol again, stir and be cooled to room temperature, uncovered standing over night, suction filtration, to the colourless .80 of filtrate ℃ vacuum-drying 8 hours, obtain mixing the about 3.02g of the thick product of porphyrin with 10ml propionic acid washing leaching cake, productive rate is 15.12%, and (amount with the pyrroles is calculated, product is with 5,10,15,20-four (4-hydroxy phenyl) porphyrin is a benchmark). silica gel (200～300 order) column chromatography for separation, with chloroform and ethanol volume ratio be 30: 1 be that eluent gets 5,10,15,20-four (4-hydroxy phenyl) porphyrin;
With 100mg (0.148mmol) 5,10,15,20-four (4-hydroxy phenyl) porphyrin and 1.0g salt of wormwood are dissolved in 20mL N, in the dinethylformamide (DMF), stir after 15 minutes, slowly drip 0.9mL 1 with 1 droplet/second speed, 6-dibromo-hexane, 20～25 ℃ of airtight stirrings of lucifuge, thin-layer chromatography is monitored to raw material point and is disappeared, after about 4 hours. stop to stir, 6 * 25mL dichloromethane extraction merges organic layer, 5 * 100mL saturated common salt water washing organic phase is to neutral, and anhydrous magnesium sulfate sealed lucifuge dry 12 hours.Filter, the organic phase rotary evaporation is concentrated into about 2mL, and silica gel column chromatography separates, and is eluent at 3: 1 with chloroform and sherwood oil volume ratio, collects first colour band, and solvent evaporated in vacuo gets bromination product, yield 86%.;
Above-mentioned brominated product is dissolved in 30mLCHCl
3In, add about 0.2g anhydrous K
2CO
3Mix the back and slowly add the 0.2mL thioacetic acid, 80 ℃ were refluxed 3 hours in the nitrogen atmosphere, be cooled to room temperature .6 * 25mL dichloromethane extraction under stirring, merge organic layer, 5 * 100mL saturated common salt water washing organic phase is to neutral, dry 12 hours of anhydrous magnesium sulfate sealing lucifuge. filter, the minimum of chloroform washing precipitation, the organic phase rotary evaporation is concentrated into about 2mL, is at 3: 1 eluent with chloroform and sherwood oil volume ratio, collect first colour band, solvent evaporated in vacuo gets the sulfo-esterification products, yield 80%.
Be mixed with the laggard nitrogen deoxidation 20min that works of mixed solvent of 20mL chloroform and 10mL methyl alcohol, more above-mentioned gained sulfo-esterification products be dissolved in this mixed solvent, other takes by weighing 1.0g KOH and is dissolved in 3mLCH
3OH and 2mL H
2O is made into 5mLKOH solution, this KOH solution is added above-mentioned mixed solvent, nitrogen atmosphere refluxed 3 hours for 80 ℃, add 100mL redistilled water termination reaction, 6 * 25mL dichloromethane extraction, merge organic layer, 5 * 100mL saturated common salt water washing organic phase is to neutral, and anhydrous magnesium sulfate sealed lucifuge dry 12 hours.Filter, merge the organic phase rotary evaporation and be concentrated into about 2mL, sherwood oil recrystallization under condition of ice bath gets 5,10,15,20-four (4-(mercapto hexane oxygen base) phenyl) porphyrin 42mg (0.0367mmol).
5,10,15 of embodiment acquisition, 20-four (4-(mercapto hexane oxygen base) phenyl) porphyrin spectral characterization is as follows:
In ultra-violet absorption spectrum, the 422nm place is the Soret band of porphyrin, 517,555,593, and the 648nm place is four Q bands of porphyrin.
In infrared spectra, at 3317cm
-1The vibration absorption peak of N-H on the porphyrin pyrrole ring appears in the place.2925,2854cm
-1Saturated C-H stretching vibration peak appears in the place; 2571cm
-1S-H stretching vibration peak, 1248cm appear in the place
-1C-O-C vibration peak, 966cm appear in the place
-1Porphyrin pyrrole ring β-H vibration peak appears in the place.
1In the HNMR spectrum, δ-2.74 place is a porphyrin ring N-H proton characteristic peak, δ 8.86 places are porphyrin ring β-H proton chemical shifts, δ 8.54-7.23 is the phenyl ring proton chemical shifts that links to each other with porphyrin, 4.28-1.25 locate to be saturated C-H proton chemical shifts, 0.88 place is a sulfydryl S-H proton chemical shifts.
Claims (1)
1, a kind of carbon chain lengths is 6 four sulfydryl porphyrins, and its structural formula is as follows:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928238A (en) * | 2017-03-09 | 2017-07-07 | 中国科学院化学研究所 | The method of break amide bonds and/or ester bond in derivatives of porphyrin and preparation method thereof and catalyst substrate pair and aqueous phase system |
| CN107759803A (en) * | 2017-11-13 | 2018-03-06 | 山东师范大学 | A kind of four sulfydryl porphyrin compounds and its production and use |
| CN110491994A (en) * | 2019-09-07 | 2019-11-22 | 苏州和颂生化科技有限公司 | End group is application of the porphyrin material of four sulfydryls in organic storage |
-
2008
- 2008-09-05 CN CN200810150905A patent/CN101665494A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928238A (en) * | 2017-03-09 | 2017-07-07 | 中国科学院化学研究所 | The method of break amide bonds and/or ester bond in derivatives of porphyrin and preparation method thereof and catalyst substrate pair and aqueous phase system |
| CN106928238B (en) * | 2017-03-09 | 2019-04-12 | 中国科学院化学研究所 | Derivatives of porphyrin and preparation method thereof and catalyst-substrate to and aqueous phase system in the method for break amide bonds and/or ester bond |
| CN107759803A (en) * | 2017-11-13 | 2018-03-06 | 山东师范大学 | A kind of four sulfydryl porphyrin compounds and its production and use |
| CN110491994A (en) * | 2019-09-07 | 2019-11-22 | 苏州和颂生化科技有限公司 | End group is application of the porphyrin material of four sulfydryls in organic storage |
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