CN102924463B - Multi-anchor self-assembled porphyrin and synthetic method thereof - Google Patents
Multi-anchor self-assembled porphyrin and synthetic method thereof Download PDFInfo
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- CN102924463B CN102924463B CN201210444326.4A CN201210444326A CN102924463B CN 102924463 B CN102924463 B CN 102924463B CN 201210444326 A CN201210444326 A CN 201210444326A CN 102924463 B CN102924463 B CN 102924463B
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Abstract
The invention discloses a multi-anchor self-assembled porphyrin and a synthetic method thereof, and belongs to the organic synthetic field. The multi-anchor self-assembled porphyrin comprises 5,15-two (4-sulfur caprylyl acyloxy phenyl) porphyrin and 5,15,20-four (4-sulfur caprylyl acyloxy phenyl). The structure of the 5,15-two (4-sulfur caprylyl acyloxy phenyl) porphyrin is shown in the description. The plane of the self-assembled porphyrin can be arranged parallel to a basement so as to facilitate to transport of electric charge.
Description
Technical field
The present invention relates to many anchors self-assembly porphyrin and synthetic method thereof, be specifically related to 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin and 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin and synthetic method thereof, belong to organic synthesis field.
Background technology
Porphyrin has good application prospect in organic electro-optic device field due to the photoelectric properties of its uniqueness and satisfactory stability.Sulfur-bearing porphyrin can form firmly Au-S covalent linkage with gold substrate, thus the self-assembled monolayer that height of formation is orderly, in order to improve the charge transport properties of gold substrate.The porphyrin with self-assembling function in document concentrates on the situation that each Porphyrin Molecule only has a sulfur-containing group, namely assemble molecule and only have an anchor of grabbing attached gold substrate, and rarely found single Porphyrin Molecule has the report of multiple anchor.In self-assembled film, the planes of molecules of single anchor porphyrin and gold substrate are generally in close to the angle of 90 degree, and angle is unfavorable for transferring charge more greatly.
Summary of the invention
All single anchor self-assembly porphyrin for the existing porphyrin with self-assembling function, be unfavorable for the problem of the transmission of electric charge in larger angle between self-assembled film mesoporphyrin molecule and substrate, the invention provides many anchors self-assembly porphyrin and synthetic method thereof, be specifically related to 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin and 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin and synthetic method thereof.Described many anchors self-assembly Porphyrin Molecule plane can be arranged in parallel with substrate, is more conducive to the transmission of electric charge.
Object of the present invention is realized by following technical scheme:
5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin, its structural formula is as follows:
The synthetic method step of described 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin is as follows:
One, the synthesis of 4-aldehyde radical phenyl lipoate
P-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide (DCC) and Dimethylamino pyridine (DMAP) are mixed, then dissolve with methylene dichloride, stir, room temperature reaction 12 ~ 14h, reacts complete, stop stirring, cross and filter insolubles, filtrate is washed, dry, except desolventizing, pillar layer separation obtains 4-aldehyde radical phenyl lipoate;
Two, the synthesis of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin
4-aldehyde radical phenyl lipoate obtained for step one, dipyrrylmethanes methylene dichloride are dissolved, then trifluoroacetic acid is added, stirring at room temperature 3h, then add DDQ (DDQ), after stirring 1h, add triethylamine termination reaction, except desolventizing, obtain solid, gained solid column chromatographic separation is obtained 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin;
Wherein, in step one, the amount of substance ratio of p-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide (DCC) and Dimethylamino pyridine (DMAP) is 1:1:1:0.5;
In step 2, the amount of substance of 4-aldehyde radical phenyl lipoate, dipyrrylmethanes, DDQ is than being 1:1:1; The amount adding trifluoroacetic acid is 5% ~ 10% of the amount of substance of 4-aldehyde radical phenyl lipoate; Add triethylamine equal with the amount of substance of trifluoroacetic acid;
Described stirring adopts convention stir mode.
5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin, its structural formula is as follows:
The synthetic method step of described 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin is as follows:
One, the synthesis of 4-aldehyde radical phenyl lipoate
P-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide (DCC) and Dimethylamino pyridine (DMAP) are mixed, then dissolve with methylene dichloride, stir, room temperature reaction 12 ~ 14h, reacts complete, stop stirring, cross and filter insolubles, filtrate is washed, dry, except desolventizing, pillar layer separation obtains 4-aldehyde radical phenyl lipoate;
Two, the synthesis of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin
The 4-aldehyde radical phenyl lipoate that step one is obtained joins in propionic acid, be heated to boiling, drip pyrroles, add rear continuation backflow 30min, then room temperature is cooled to, produce precipitation, by described sedimentation and filtration, successively by saturated solution of sodium bicarbonate and distilled water wash precipitation, vacuum-drying precipitation obtains 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin;
Wherein, in step one, the amount of substance ratio of p-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide (DCC) and Dimethylamino pyridine (DMAP) is 1:1:1:0.5;
In step 2, the amount of substance of 4-aldehyde radical phenyl lipoate, pyrroles is than being 1:1;
Described stirring adopts convention stir mode.
Beneficial effect
(1) many anchors self-assembly porphyrin 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin of the present invention and 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin, can be used for the preparation of self-assembled monolayer.And many anchors Porphyrin Molecule plane can be arranged in parallel with substrate, be more conducive to the transmission of electric charge.
(2) many anchors self-assembly porphyrin of the present invention can be used for organic light emitting diode as electrode modified material, the field such as organic field effect tube and organic solar batteries.
Accompanying drawing explanation
Fig. 1 is the synthetic method chemical equation of described 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin;
Fig. 2 is the synthetic method chemical equation of described 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin;
Wherein, in Fig. 1, TFA is triethylamine, and rt represents room temperature.
Embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited thereto.
Embodiment 1
The synthetic method of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin, as shown in Figure 1, step is as follows for described method chemical equation:
One, the synthesis of 4-aldehyde radical phenyl lipoate
P-Hydroxybenzaldehyde 488mg (4mmol), Thioctic Acid 906mg (4.4mmol), DCC988.8mg (4.8mmol), DMAP244mg (2mmol) is added successively in 200ml there-necked flask, then in system, 160ml methylene dichloride is added, induction stirring, room temperature reaction 14h, thin-layer chromatography (TLC) monitoring reaction, react complete, stop stirring, cross and filter insolubles, filtrate washes three times, dried over mgso, pressure reducing and steaming solvent, methylene dichloride crosses post, obtains yellow oily liquid 1104mg, and productive rate is 89%.Carrying out proton nmr spectra to gained yellow oily liquid characterizes as follows:
1h-NMR (400M, CDCl
3): δ 9.995 (s, 1H, CHO), 7.934 (d, 2H, phenyl), 7.285 (d, 2H, phenyl), 3.6 (m, 3H, CH
2s), 3.2 (m, 2H, CH
2cO), 2.6 (m, CH
2), 2.49 (m, CH
2cH
2), 1.81 (m, (CH
2), conform to expected structure, namely described yellow oily liquid is 4-aldehyde radical phenyl lipoate of the present invention.
Two, the synthesis of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin
By 500ml methylene dichloride, 657mg(2.12mmol) 4-aldehyde radical phenyl lipoate, 310mg(2.12mmol) dipyrrylmethanes joins in 1000ml there-necked flask; react under nitrogen protection; add 0.1ml(1.35mmol after logical nitrogen 30min) trifluoroacetic acid; room temperature induction stirring 3h; then add 502mg(2.22mmol) DDQ; after stirring 1h, add the triethylamine termination reaction of 1.55ml.Removal of solvent under reduced pressure, silicagel column methylene dichloride (DCM)/sherwood oil (PE)=3:1 crossed by gained solid, and Rf value (Rf) ≈ 0.4, obtains violet solid 462mg, and productive rate is 50%.Sign carried out to gained violet solid as follows: proton nmr spectra:
1h-NMR (400M, CDCl
3): δ 10.332 (s, 2H, CH pyrroles ortho position), 9.4 (d, 4H, pyrroles H), 9.1 (d, 4H, pyrroles H), 8.29 (d, 4H, phenyl H), 7.56 (d, 4H, phenyl), 3.7 (m, 3H, CH
2s), 3.274 (m, 2H, CH
2cO), 2.8 (m, CH
2), 2.587 (m, CH
2cH
2), 2.04 (m, (CH
2) ,-3.144 (s, 2H, NH).Mass spectrum (MALDI-TOF ionization method): 871.3 (MH
+).Can judge thus, described violet solid is 5,15-bis-(the pungent phenyl of 4-sulphur) of the present invention porphyrin.
Embodiment 2
The synthetic method of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin, as shown in Figure 1, step is as follows for described method chemical equation:
One, the synthesis of 4-aldehyde radical phenyl lipoate
Adopt the method synthesis 4-aldehyde radical phenyl lipoate 328mg of step one in embodiment 1, difference: the reaction times will replace with 12h.
Two, the synthesis of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin
By 250ml methylene dichloride, 328mg(1.06mmol) 4-aldehyde radical phenyl lipoate, 155mg(1.06mmol) dipyrrylmethanes joins in 500ml there-necked flask; react under nitrogen protection; add 0.1ml(1.35mmol after logical nitrogen 30min) trifluoroacetic acid; room temperature induction stirring 3h; then add 250mg(1.11mmol) DDQ; after stirring 1h, add the triethylamine termination reaction of 2ml.Removal of solvent under reduced pressure, silicagel column DCM/PE=3:1 crossed by gained solid, Rf ≈ 0.4, obtains violet solid 240mg, and productive rate is 52%.Characterize described violet solid, proton nmr spectra and mass-spectrometric data show to conform to expected structure, and described violet solid is 5,15-bis-(the pungent phenyl of 4-sulphur) of the present invention porphyrin.
Embodiment 3
The synthetic method of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin, as shown in Figure 1, step is as follows for described method chemical equation:
One, the synthesis of 4-aldehyde radical phenyl lipoate
Adopt the method synthesis 4-aldehyde radical phenyl lipoate 1.3g of step one in embodiment 1, difference: the reaction times will replace with 13h.
Two, the synthesis of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin
By 500ml methylene dichloride, 1.3g(4.2mmol) 4-aldehyde radical phenyl lipoate, 612mg(4.2mmol) dipyrrylmethanes joins in 1000ml there-necked flask; react under nitrogen protection; add 0.1ml(1.35mmol after logical nitrogen 30min) trifluoroacetic acid; room temperature induction stirring 3h; then add 1.0g(4.2mmol) DDQ; after stirring 1h, add the triethylamine termination reaction of 4ml.Removal of solvent under reduced pressure, silicagel column DCM/PE=3:1 crossed by gained solid, Rf ≈ 0.4, obtains violet solid 841mg, and productive rate is 46%.Characterize described violet solid, proton nmr spectra and mass-spectrometric data show to conform to expected structure, and described violet solid is 5,15-bis-(the pungent phenyl of 4-sulphur) of the present invention porphyrin.
Embodiment 4
The synthetic method of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin, as shown in Figure 2, step is as follows for described method chemical equation:
One, the synthesis of 4-aldehyde radical phenyl lipoate
Adopt the method synthesis 4-aldehyde radical phenyl lipoate 3.1g of step one in embodiment 1.
Two, the synthesis of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin
In the 500ml there-necked flask that reflux condensing tube is housed, add 3.1g (10mmol) 4-aldehyde radical phenyl lipoate, 200ml propionic acid, be heated to boil (145 DEG C), now solution is glassy yellow, pyrroles 0.7ml(10mmol is dripped) in system, 30min adds, solution colour by glassy yellow through orange red, red-brown, finally become brownish black, continue backflow 30min, after boiling stops, while hot solution is gone in large beaker, naturally cool to room temperature, produce precipitation,-5 DEG C of cool overnight, Büchner funnel filtration under diminished pressure, successively by saturated solution of sodium bicarbonate and distilled water wash precipitation, vacuum-drying precipitates, obtain violet solid 1.6g, productive rate is 45%.
Sign carried out to gained violet solid as follows: as shown in Figure 1, proton nmr spectra:
1h-NMR (400M, CDCl
3): δ 8.87 (s, 8H, pyrroles H), 8.2 (d, 8H, phenyl H), 7.5 (d, 8H, phenyl), 3.68 (m, 3H, CH
2s), 3.2 (m, 2H, CH
2cO) ,-3.21 (s, 2H, NH).Mass spectrum (MALDI-TOF ionization method): 1431.6 (MH
+).Can judge thus, described violet solid is 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) of the present invention porphyrin.
Embodiment 5
The synthetic method of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin, as shown in Figure 2, step is as follows for described method chemical equation:
One, the synthesis of 4-aldehyde radical phenyl lipoate
Adopt the method synthesis 4-aldehyde radical phenyl lipoate 1.55g of step one in embodiment 1, difference: the reaction times will replace with 13h.
Two, the synthesis of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin
In the 250ml there-necked flask that reflux condensing tube is housed, add 1.55g (5.0mmol) 4-aldehyde radical phenyl lipoate, 100ml propionic acid, be heated to boil (145 DEG C), now solution is glassy yellow, pyrroles 0.35ml(5.0mmol is dripped) in system, 30min adds, solution colour by glassy yellow through orange red, red-brown, finally become brownish black, continue backflow 30min, after boiling stops, while hot solution is gone in large beaker, naturally cool to room temperature, produce precipitation,-5 DEG C of cool overnight, Büchner funnel filtration under diminished pressure, successively by saturated solution of sodium bicarbonate and distilled water wash precipitation, vacuum-drying precipitates, obtain violet solid 913mg, productive rate is 51%.Characterize described violet solid, proton nmr spectra and mass-spectrometric data show to conform to expected structure, and described violet solid is 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) of the present invention porphyrin.
Embodiment 6
The synthetic method of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin, as shown in Figure 2, step is as follows for described method chemical equation:
One, the synthesis of 4-aldehyde radical phenyl lipoate
Adopt the method synthesis 4-aldehyde radical phenyl lipoate 6.2g of step one in embodiment 1, difference: the reaction times will replace with 12h.
Two, the synthesis of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin
In the 500ml there-necked flask that reflux condensing tube is housed, add 6.2g (20mmol) 4-aldehyde radical phenyl lipoate, 200ml propionic acid, be heated to boil (145 DEG C), now solution is glassy yellow, pyrroles 1.4ml(20mmol is dripped) in system, 30min adds, solution colour by glassy yellow through orange red, red-brown, finally become brownish black, continue backflow 30min, after boiling stops, while hot solution is gone in large beaker, naturally cool to room temperature, produce precipitation,-5 DEG C of cool overnight, Büchner funnel filtration under diminished pressure, successively by saturated solution of sodium bicarbonate and distilled water wash precipitation, vacuum-drying precipitates, obtain violet solid 3.0g, productive rate is 42%.Characterize described violet solid, proton nmr spectra and mass-spectrometric data show to conform to expected structure, and described violet solid is 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) of the present invention porphyrin.
The present invention includes but be not limited to above embodiment, every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.
Claims (4)
1.5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin, is characterized in that: described 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin structure formula is as follows:
2. the synthetic method of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin according to claim 1, is characterized in that: described method steps is as follows:
One, the synthesis of 4-aldehyde radical phenyl lipoate
P-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide and Dimethylamino pyridine are mixed, then dissolve with methylene dichloride, stir, room temperature reaction 12 ~ 14h, reacts complete, stop stirring, cross and filter insolubles, filtrate is washed, dry, except desolventizing, pillar layer separation obtains 4-aldehyde radical phenyl lipoate;
Two, the synthesis of 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin
4-aldehyde radical phenyl lipoate obtained for step one, dipyrrylmethanes methylene dichloride are dissolved, then trifluoroacetic acid is added, stirring at room temperature 3h, then add DDQ, after stirring 1h, add triethylamine termination reaction, except desolventizing, obtain solid, gained solid column chromatographic separation is obtained 5,15-bis-(the pungent phenyl of 4-sulphur) porphyrin;
In described step one, the amount of substance of p-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide and Dimethylamino pyridine is than being 1:1:1:0.5;
In described step 2, the amount of substance of 4-aldehyde radical phenyl lipoate, dipyrrylmethanes, DDQ is than being 1:1:1;
The amount adding trifluoroacetic acid in described step 2 is 5% ~ 10% of the amount of substance of 4-aldehyde radical phenyl lipoate;
Triethylamine is added equal with the amount of substance of trifluoroacetic acid in described step 2.
3.5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin, is characterized in that: described 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin structure formula is as follows:
4. the synthetic method of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin according to claim 3, is characterized in that: described method steps is as follows:
One, the synthesis of 4-aldehyde radical phenyl lipoate
P-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide and Dimethylamino pyridine are mixed, then dissolve with methylene dichloride, stir, room temperature reaction 12 ~ 14h, reacts complete, stop stirring, cross and filter insolubles, filtrate is washed, dry, except desolventizing, pillar layer separation obtains 4-aldehyde radical phenyl lipoate;
Two, the synthesis of 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin
The 4-aldehyde radical phenyl lipoate that step one is obtained joins in propionic acid, be heated to boiling, drip pyrroles, add rear continuation backflow 30min, then room temperature is cooled to, produce precipitation, by described sedimentation and filtration, successively by saturated solution of sodium bicarbonate and distilled water wash precipitation, vacuum-drying precipitation obtains 5,10,15,20-tetra-(the pungent phenyl of 4-sulphur) porphyrin;
In described step one, the amount of substance of p-Hydroxybenzaldehyde, Thioctic Acid, dicyclohexylcarbodiimide and Dimethylamino pyridine is than being 1:1:1:0.5;
In described step 2, the amount of substance of 4-aldehyde radical phenyl lipoate, pyrroles is than being 1:1.
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