CN104592228A - Fullerene-perylene functional molecule and preparation method thereof - Google Patents
Fullerene-perylene functional molecule and preparation method thereof Download PDFInfo
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract
The invention discloses a fullerene-perylene functional molecule and a preparation method thereof, and relates to the technical field of design and synthesis of functional organic molecules. In a structural general formula, two fullerene pyrrole ring compounds with the same structure are symmetrically connected on two anhydrides of perylene dianhydride by a rigid benzidine structure, benzidine is positioned at an axial position of a fullerene pyrrole ring structure, and thus a rigid linear molecule is formed. Firstly, one amino group of benzidine is protected by BOC, BOC protected benzidine is generated and then undergoes a reaction with bromine alkyl acetate, and the product is subjected to a Prato reaction with C60 and glyoxylic acid alkyl ester to synthesize a BOC protected fullerene N-hetero five-membered ring compound, followed by, a BOC protecting group is removed to generate a fullerene N-hetero five-membered ring compound containing an amino active group, and finally the fullerene N-hetero five-membered ring compound is subjected to an amidation reaction with perylene dianhydride to synthesize the functional molecule. The functional molecule can be applied in the fields of organic solar cells, photodynamic therapy and tribology.
Description
Technical field
The present invention relates to functional organic molecule Design and synthesis technical field, specifically relate to a kind of soccerballene-perylene functional molecular and preparation method thereof.
Background technology
Since soccerballene is found (Kroto, H.W.; Heath, J.R.; O ' Brien, S.C.; Curl, R.F.; Smalley, R.E.Nature 1985,318,162.) and be successfully separated (
w.; Lamb, L.D.; Fostiropoulos, K.; Huffman, D.R.Nature 1990,347,354.) since, it has caused the attention of more and more scientist.Due to C
60special geometric configuration, it shows much special character, such as supraconductivity, magnetic, lubrication, electricity, electrochemistry and optical property etc.Fullerene compound can also be used for the DNA cleavage that light promotes, enzyme inhibitors, and the aspect such as cytotoxicity experiment.But due to C
60absorption in visible region is very weak, only occurs a very weak absorption, because which limit it in very many-sided application at 700nm.If can at C
60on be connected to the chromophoric group that visible region has higher molar extinction coefficient, catch feeler as light, just can improve the absorption of molecule to visible ray widely.
Perylene compounds is also made up of two additional phenyl ring of naphthalene nucleus together, this compounds has stronger absorption in 400 ~ 700nm interval, energy ~ the 54kcal/mol of their excited singlet state, fluorescence quantum yield is greater than 0.93, maximum absorption wavelength ~ the 500nm of triplet state-triplet state, molar extinction coefficient ~ 6 × 10
-4m
-1cm
-1(Ford, W.E.; Kamat, P.V.; J.Phys.Chem.1987,91,6373.), simultaneously they also tool from good photo and thermal stability, be therefore widely used in field-effect transistor, electroluminescent device and solar energy converting aspect.But, because such planes of molecules is better, there is stronger π-π stacking effect, be therefore easy to assemble in liquid phase, affect the application of molecule.
Summary of the invention
In order to overcome the above-mentioned defect existed in prior art, an object of the present invention is to provide a kind of soccerballene-perylene functional molecular, and it both can stop the stacking of molecule effectively, can also make up C
60absorb weak shortcoming in visible region, form novel functional molecular system.
For realizing this object, present invention employs following technical scheme:
A kind of soccerballene-perylene functional molecular, its general formula of molecular structure is as follows:
In general formula, R is selected from the alkyl that carbonatoms is 1 ~ 12;
In general formula, X is H, Cl, Br ,-NR
1r
2,-OR
1or SR
1, wherein R
1be selected from the aryl of replacement or heterocyclic aryl, carbonatoms is the alkyl of 2 ~ 12, R
2for H or carbonatoms are the alkyl of 2 ~ 12, and work as R
1when being selected from aryl or the heterocyclic aryl of replacement, R
2for H;
In general formula, Y is H, Cl, Br ,-NR
3r
4,-OR
3or SR
3, wherein R
3be selected from the aryl of replacement or heterocyclic aryl, carbonatoms is the alkyl of 2 ~ 12, R
4for H or carbonatoms are the alkyl of 2 ~ 12, and work as R
3when being selected from aryl or the heterocyclic aryl of replacement, R
4for H;
Be selected from when in general formula, X, Y are different H, Cl, Br atom (when X be in H, Cl, Br atom any one time, Y is-NR
3r
4,-OR
3, SR
3in any one, vice versa).
In above formula, the soccerballene pyrrole ring compound of two same structures is connected on two acid anhydrides of perylene dicarboxylic anhydride by the p-diaminodiphenyl symmetrical configuration of rigidity, and p-diaminodiphenyl is the axial location in soccerballene pyrrole ring structure, thus form the thread-like molecule of a rigidity.
Another object of the present invention is to the preparation method that a kind of soccerballene-perylene functional molecular is provided, for realizing this object, present invention employs following technical scheme:
The preparation method of soccerballene-perylene functional molecular, syntheti c route as shown in Figure 1, in turn includes the following steps:
Step is 1.: p-diaminodiphenyl and tert-Butyl dicarbonate and Boc
2there is the compound 1 that substitution reaction preparation has monolateral Boc protecting group in O, the mol ratio of p-diaminodiphenyl and tert-Butyl dicarbonate is 0.8 ~ 1.2: 0.8 ~ 1.2, and temperature of reaction is room temperature, and the reaction times is 12 ~ 36h;
Step is 2.: compound 1 under the katalysis of Anhydrous potassium carbonate with alkyl bromoacetate and BrCH
2cO
2there is substitution reaction and prepare compound 2 in R, the mol ratio of compound 1, Anhydrous potassium carbonate and alkyl bromoacetate is 0.8 ~ 1.2: 1.2 ~ 2.0: 0.8 ~ 1.2, and temperature of reaction is room temperature, and the reaction times is 10 ~ 24h;
Step is 3.: compound 2, soccerballene and C
60with oxoethanoic acid alkyl ester and HCOCO
2there is Prato reaction and prepare compound 3 in R, the mol ratio of compound 2, soccerballene and oxoethanoic acid alkyl ester is 1.8 ~ 2.2: 0.8 ~ 1.2: 1.6 ~ 12, and temperature of reaction is 140 ~ 160 DEG C, and the reaction times is 0.5 ~ 5h;
Step is 4.: compound 3 removes Boc protecting group and prepares compound 4 in chloroform-trifluoroacetic acid solvent system, and temperature of reaction is room temperature, and the reaction times is 0.5 ~ 5h;
Step is 5.: compound 4 amidate action occurs with compound 5 under Catalyzed by Imidazole and prepares target product P and soccerballene-perylene functional molecular, compound 4, compound 5 are 2.8 ~ 3.2: 1: 10 ~ 15 with the mol ratio of imidazoles, temperature of reaction is 70 ~ 90 DEG C, and the reaction times is 3 ~ 7 days.
Further improvement as the preparation method of soccerballene of the present invention-perylene functional molecular:
Described step 1. concrete operations is: be first dissolved in Isosorbide-5-Nitrae-dioxane by p-diaminodiphenyl with 1: 15 ~ 25 (g: mL), under argon shield, stir 5 ~ 40min; Again by Boc
2o is dissolved in Isosorbide-5-Nitrae-dioxane with 1: 4 ~ 6 (g: mL), is added drop-wise in p-diaminodiphenyl solution lentamente with constant pressure funnel, and whole dropping process control is within 30min; Mixed solution is stirring reaction at room temperature, utilizes thin-layer chromatography to follow the tracks of, until the content of target product is greater than 80%, and stopped reaction; After having reacted; revolve except the solvent in system, thick product is crossed post and is separated, and eluent is sherwood oil: ethyl acetate=4: the mixed solvent of 1 (V: V); collect second colour band, finally concentrated, vacuum-drying must have the compound 1 of monolateral Boc protecting group.
Described step 2. concrete operations is: compound 1 is dissolved in DMF with 1: 1.5 ~ 2.5 (g: mL), and then adds anhydrous K
2cO
3; Reaction mixture at room temperature first leads to argon shield 5 ~ 40min, then promptly adds BrCH
2cO
2r, continues logical 5 ~ 20min argon gas, is sealed by reaction flask; Reaction mixture is placed on stirred at ambient temperature 10 ~ 24h, utilizes thin-layer chromatography to follow the tracks of, and treats that raw material point disappears substantially, decompression removing DMF, then mixture is crossed post separation, obtains compound 2.
Described step 3. concrete operations is: by C
60be dissolved in orthodichlorobenzene with 1: 50 ~ 55 (g: mL), and add compound 2; At room temperature, logical argon shield 20 ~ 80min, then by HCOCO for reaction mixture
2r adds, and continues logical 5 ~ 20min argon gas, reaction mixture is put into the oil bath pan being heated to 140 ~ 160 DEG C in advance and react; When the amount residue 30 ~ 40% of soccerballene, stopped reaction; Then underpressure distillation, by the orthodichlorobenzene removing in reaction system; Reaction mixture dithiocarbonic anhydride dissolves, and with pillar layer separation, first using dithiocarbonic anhydride as eluent, removes the C that unreacted is complete
60, and then use the eluent of large polarity instead, obtain compound 3.
Described step 4. concrete operations is: be dissolved in chloroform by compound 3 with 1: 110 ~ 130 (g: mL), reaction solution is under the protection of argon gas, in stirred at ambient temperature 5 ~ 20min, then the trifluoroacetic acid that to add with 1: 15 ~ 25 (g: mL) be proportional, reaction solution is stirring reaction 0.5 ~ 5h at room temperature, thin-layer chromatography is utilized to follow the tracks of, after the completely dissolve of compound 3 raw material point, stopped reaction; Solvent is spin-dried for, and filters with silicagel column, obtain brown color compound 4.
Described step 5. concrete operations is: be dissolved in chloroform by compound 4 with 1: 150 ~ 200 (g: mL), add compound 5 and imidazoles again, reaction mixture first at room temperature logical argon gas 5 ~ 20min, and then be placed on be heated to 70 ~ 90 DEG C in advance oil bath pan in react; Utilize thin-layer chromatography to follow the tracks of, treat that compound 5 is basic and consume completely, stopped reaction, after reaction solution is cooled to room temperature, with chloroform and water extraction, organic phase anhydrous sodium sulfate drying, then revolves and desolventizes, and crosses post separation and obtains garnet target product P.
Compared with prior art, beneficial effect of the present invention shows:
1), the present invention is connected on soccerballene by appropriate design by having the comparatively strong perylene absorbed in visible region, not only makes up soccerballene C
60absorb weak weakness in visible region, and overcome the stack effect of perylene in liquid phase, to form novel functional molecular system.
2), this soccerballene-perylene functional molecular can be used as acceptor material, is applied to organic solar batteries field; Also as the triplet state photosensitization molecule not containing heavy atom, the fields such as photodynamic therapy can be applied to; As lubricating oil additive, tribological field can also be applied to.
3), the preparation method of soccerballene-perylene functional molecular, technique is simple, and reaction fast, is applicable to batch production.
Accompanying drawing explanation
Fig. 1 is the syntheti c route figure of soccerballene-perylene functional molecular.
Fig. 2 is a kind of soccerballene-perylene functional molecular P1 prepared by embodiment
1h NMR.
Fig. 3 is a kind of soccerballene-perylene functional molecular P1 prepared by embodiment
13c NMR.
Embodiment
The present embodiment, for a kind of soccerballene-perylene functional molecular P1, introduces its structure and concrete preparation method in conjunction with syntheti c route figure (shown in Fig. 1).
Step 1.
First getting 8.4mmol p-diaminodiphenyl is dissolved in the Isosorbide-5-Nitrae-dioxane of 30mL, under argon shield, stir 30min.Again by 8.4mmol tert-Butyl dicarbonate and Boc
2o is dissolved in the Isosorbide-5-Nitrae-dioxane of 10mL, is added drop-wise in p-diaminodiphenyl solution lentamente with constant pressure funnel, and whole dropping process control is within 30min.Mixed solution is stirring reaction at room temperature, utilizes thin-layer chromatography to follow the tracks of, and after 24h, the content of target product is greater than 80%, stopped reaction.Revolve except the solvent in system; thick product is crossed post and is separated; using sherwood oil: ethyl acetate=4: 1 (V: V), as eluent, collects second colour band, finally concentrated, vacuum-drying obtains the compound 1 (85%) that 2.02g has monolateral Boc protecting group
Step 2.
Get 2.6mmol compound 1 and put into 25mL single port bottle, and dissolve in order to the DMF of 1.5mL, and then add 4.5mmol anhydrous K
2cO
3.Reaction mixture at room temperature first leads to argon shield 30min, then promptly adds ethyl bromoacetate and BrCH
2cO
2et, continues logical 10min argon gas, is sealed by single port bottle.Reaction mixture is placed on stirred at ambient temperature, utilizes thin-layer chromatography to follow the tracks of, and after 11h, raw material point disappears substantially, decompression removing DMF, then mixture is crossed post separation, obtains 0.66g compound 2 (68%).
Step 3.
By 0.44mmol compound 2 and 0.22mmol soccerballene C
60be dissolved in the orthodichlorobenzene of 8mL.At room temperature, logical argon shield 60min, then by glyoxylic acid ethyl ester and HCOCO for reaction mixture
2et adds, and continues logical 10min argon gas, reaction mixture is put into the oil bath pan being heated to 150 DEG C in advance and react.When after 1.5h, the amount of soccerballene remains 30 ~ 40%, stopped reaction.Then underpressure distillation, by the orthodichlorobenzene removing in reaction system.Reaction mixture dithiocarbonic anhydride dissolves, and with pillar layer separation, first using dithiocarbonic anhydride as eluent, removes the C that unreacted is complete
60, and then use the eluent of large polarity instead, obtain 86.9mg compound 3 the soccerballene N-of the Boc protection (mix 5-membered ring compounds) (35%).
Step 4.
Getting 0.09mmol compound 3 is dissolved in the chloroform of 12mL, reaction solution under the protection of argon gas, in stirred at ambient temperature 10min; then add the trifluoroacetic acid of 2mL, reaction solution is stirring reaction at room temperature, utilizes thin-layer chromatography to follow the tracks of; compound 3 raw material point completely dissolve after 1.5h, stopped reaction.Solvent is spin-dried for, and filters with silicagel column, obtain 87.6mg brown color compound 4 (the soccerballene N-containing amino active group mix 5-membered ring compounds) (95%).
Step 5.
Add in the two-mouth bottle of 25mL by 0.06mmol compound 4 and 0.02mmol perylene dicarboxylic anhydride 5 and 2.25mmol imidazoles, the chloroform then adding 10mL dissolves.Reaction mixture first at room temperature logical argon gas 10min, and then be placed on be heated to 80 DEG C in advance oil bath pan in react.Utilize thin-layer chromatography to follow the tracks of, react compound 5 after 5 days and substantially consume completely, stopped reaction, after reaction solution is cooled to room temperature, with chloroform and water extraction, organic phase anhydrous sodium sulfate drying, then revolve and desolventize, cross post separation and obtain 29.7mg garnet target product P1 (44%).
The structural formula of perylene dicarboxylic anhydride 5 is as follows:
The target product P1's that above-described embodiment system is each
1h NMR,
13c NMR distinguishes as shown in Figure 2,3, the mass-spectrometric data of this molecule of experiment test: m/z=3098.2965 (C
224h
96n
4o
16, M
+).
The structural formula of target product P1 is as follows:
To those skilled in the art, along with the different choice of R, X, Y in target product P (general structure is as follows) general formula, the soccerballene-perylene functional molecular of several different structure will be prepared,
Example 1 (soccerballene-perylene functional molecular P2):
In general formula, R is methyl, and X is H, Y is-NR
3h, wherein R
3for isobutyl-.
Example 2 (soccerballene-perylene functional molecular P3):
In general formula, R is sec.-propyl, and X is Br, Y is SR
3, wherein R
3for the aryl replaced.
Example 3 (soccerballene-perylene functional molecular P4):
In general formula, R is dodecyl, and Y is Cl, X is-NR
1r
2, wherein R
1for the heterocyclic aryl replaced, R
2for H.
Example 4 (soccerballene-perylene functional molecular P5):
In general formula, R is normal-butyl, X and Y is-NR
1r
2, wherein R
1for ethyl, R
2for H.
Example 5 (soccerballene-perylene functional molecular P6):
In general formula, R is methyl, and X is-OR
1, wherein R
1for the aryl replaced.
Y is-NR
3r
4, wherein R
3for the aryl replaced, R
4for H.
Example 6 (soccerballene-perylene functional molecular P7):
In general formula, R is n-hexyl, and X is-NR
1r
2, wherein R
1=R
2=-CH
2cH
2cH
2cH
2cH
2.
Y is H.
Above-mentioned different soccerballene-perylene functional molecular (P2-P7), its preparation method and reaction mechanism and P1 comparatively identical, this is no longer going to repeat them.
Claims (7)
1. soccerballene-perylene functional molecular, its general formula of molecular structure is as follows:
In general formula, R is selected from the alkyl that carbonatoms is 1 ~ 12;
In general formula, X is H, Cl, Br ,-NR
1r
2,-OR
1or SR
1, wherein R
1be selected from the aryl of replacement or heterocyclic aryl, carbonatoms is the alkyl of 2 ~ 12, R
2for H or carbonatoms are the alkyl of 2 ~ 12, and work as R
1when being selected from aryl or the heterocyclic aryl of replacement, R
2for H;
In general formula, Y is H, Cl, Br ,-NR
3r
4,-OR
3or SR
3, wherein R
3be selected from the aryl of replacement or heterocyclic aryl, carbonatoms is the alkyl of 2 ~ 12, R
4for H or carbonatoms are the alkyl of 2 ~ 12, and work as R
3when being selected from aryl or the heterocyclic aryl of replacement, R
4for H;
H, Cl, Br atom is selected from when X, Y are different in general formula.
2. a preparation method for soccerballene-perylene functional molecular as claimed in claim 1, is characterized in that: syntheti c route as shown in Figure 1, in turn includes the following steps:
Step is 1.: p-diaminodiphenyl and tert-Butyl dicarbonate and Boc
2there is the compound 1 that substitution reaction preparation has monolateral Boc protecting group in O, the mol ratio of p-diaminodiphenyl and tert-Butyl dicarbonate is 0.8 ~ 1.2: 0.8 ~ 1.2, and temperature of reaction is room temperature, and the reaction times is 12 ~ 36h;
Step is 2.: compound 1 under the katalysis of Anhydrous potassium carbonate with alkyl bromoacetate and BrCH
2cO
2there is substitution reaction and prepare compound 2 in R, the mol ratio of compound 1, Anhydrous potassium carbonate and alkyl bromoacetate is 0.8 ~ 1.2: 1.2 ~ 2.0: 0.8 ~ 1.2, and temperature of reaction is room temperature, and the reaction times is 10 ~ 24h;
Step is 3.: compound 2, soccerballene and C
60with oxoethanoic acid alkyl ester and HCOCO
2there is Prato reaction and prepare compound 3 in R, the mol ratio of compound 2, soccerballene and oxoethanoic acid alkyl ester is 1.8 ~ 2.2: 0.8 ~ 1.2: 1.6 ~ 12, and temperature of reaction is 140 ~ 160 DEG C, and the reaction times is 0.5 ~ 5h;
Step is 4.: compound 3 removes Boc protecting group and prepares compound 4 in chloroform-trifluoroacetic acid solvent system, and temperature of reaction is room temperature, and the reaction times is 0.5 ~ 5h;
Step is 5.: compound 4 amidate action occurs with compound 5 under Catalyzed by Imidazole and prepares target product P and soccerballene-perylene functional molecular, compound 4, compound 5 are 2.8 ~ 3.2: 1: 10 ~ 15 with the mol ratio of imidazoles, temperature of reaction is 70 ~ 90 DEG C, and the reaction times is 3 ~ 7 days.
3. the preparation method of soccerballene according to claim 2-perylene functional molecular, it is characterized in that: described step 1. concrete operations is: first p-diaminodiphenyl is dissolved in 1 with 1: 15 ~ 25 (g: mL), in 4-dioxane, under argon shield, stir 5 ~ 40min; Again by Boc
2o is dissolved in Isosorbide-5-Nitrae-dioxane with 1: 4 ~ 6 (g: mL), is added drop-wise in p-diaminodiphenyl solution lentamente with constant pressure funnel, and whole dropping process control is within 30min; Mixed solution is stirring reaction at room temperature, utilizes thin-layer chromatography to follow the tracks of, until the content of target product is greater than 80%, and stopped reaction; After having reacted; revolve except the solvent in system, thick product is crossed post and is separated, and eluent is sherwood oil: ethyl acetate=4: the mixed solvent of 1 (V: V); collect second colour band, finally concentrated, vacuum-drying must have the compound 1 of monolateral Boc protecting group.
4. the preparation method of soccerballene according to claim 2-perylene functional molecular, is characterized in that: described step 2. concrete operations is: get compound 1 and be dissolved in DMF with 1: 1.5 ~ 2.5 (g: mL), and then add anhydrous K
2cO
3; Reaction mixture at room temperature first leads to argon shield 5 ~ 40min, then promptly adds BrCH
2cO
2r, continues logical 5 ~ 20min argon gas, is sealed by reaction flask; Reaction mixture is placed on stirred at ambient temperature 10 ~ 24h, utilizes thin-layer chromatography to follow the tracks of, and treats that raw material point disappears substantially, decompression removing DMF, then mixture is crossed post separation, obtains compound 2.
5. the preparation method of soccerballene according to claim 2-perylene functional molecular, is characterized in that: described step 3. concrete operations is: by C
60be dissolved in orthodichlorobenzene with 1: 50 ~ 55 (g: mL), and add compound 2; At room temperature, logical argon shield 20 ~ 80min, then by HCOCO for reaction mixture
2r adds, and continues logical 5 ~ 20min argon gas, reaction mixture is put into the oil bath pan being heated to 140 ~ 160 DEG C in advance and react; When the amount residue 30 ~ 40% of soccerballene, stopped reaction; Then underpressure distillation, by the orthodichlorobenzene removing in reaction system; Reaction mixture dithiocarbonic anhydride dissolves, and with pillar layer separation, first using dithiocarbonic anhydride as eluent, removes the C that unreacted is complete
60, and then use the eluent of large polarity instead, obtain compound 3.
6. the preparation method of soccerballene according to claim 2-perylene functional molecular, it is characterized in that: described step 4. concrete operations is: compound 3 is dissolved in chloroform with 1: 110 ~ 130 (g: mL), reaction solution is under the protection of argon gas, in stirred at ambient temperature 5 ~ 20min, then the trifluoroacetic acid that to add with 1: 15 ~ 25 (g: mL) be proportional, reaction solution is stirring reaction 0.5 ~ 5h at room temperature, thin-layer chromatography is utilized to follow the tracks of, after the completely dissolve of compound 3 raw material point, stopped reaction; Solvent is spin-dried for, and filters with silicagel column, obtain brown color compound 4.
7. the preparation method of soccerballene according to claim 2-perylene functional molecular, it is characterized in that: described step 5. concrete operations is: compound 4 is dissolved in chloroform with 1: 150 ~ 200 (g: mL), add compound 5 and imidazoles again, reaction mixture first at room temperature logical argon gas 5 ~ 20min, and then be placed on be heated to 70 ~ 90 DEG C in advance oil bath pan in react; Utilize thin-layer chromatography to follow the tracks of, treat that compound 5 is basic and consume completely, stopped reaction, after reaction solution is cooled to room temperature, with chloroform and water extraction, organic phase anhydrous sodium sulfate drying, then revolves and desolventizes, and crosses post separation and obtains garnet target product P.
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