CN101289447B - Trifluoromethyl substituted perylene bis diimines and preparation method thereof - Google Patents
Trifluoromethyl substituted perylene bis diimines and preparation method thereof Download PDFInfo
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Abstract
The invention provides a category of perylene derivatives, that is perylene two-diimine replaced by trifluoromethyl and a preparation method thereof; wherein, the method comprises that perylene four-formate is used as the raw material to synthesize bromination perylene four-formate by brominating liquid bromine; the bromination perylene four-formate and perfluorinated iodoalkane are used as the raw materials to synthesize the perylene four-formate replaced by long chain perfluoroalkyl under the catalysis of copper powders or copper-tin alloy powder, and the bromination perylene four-formate and sodium trifluoroacetate are used as the raw materials to synthesize the perylene four-formate replaced by the trifluoromethyl under the catalysis of cuprous iodide; the long chain perfluoroalkyl or the perylene four-formate replaced by the trifluoromethyl is used as the raw material and hydrolyzed to synthesize the perylene four-formate or perylene four-formate anhydride replaced by the perfluoroalkyl under the function of inorganic alkali or chlorosulfonic acid; the perylene four-formate replaced by the trifluoroacetate and alkylamine or aniline are used as the raw material to synthesize the perylene two-diimine replaced by the trifluoromethyl .
Description
Technical field
Perylene bis diimines that perylene tetracarboxylic acid that the perylene tetramethyl acid esters that the present invention relates to and the derivative bromine of perylene replaces for perylene tetramethyl acid esters, perfluoroalkyl, perfluoroalkyl replace and trifluoromethyl replace and preparation method thereof belongs to organic chemical industry and fine chemical technology field.
Background technology
3,4,9, the basic material of 10-3,4, 9, 10-perylenetetracarboxylic dianhydride Shi perylene pigments, dyestuff and organic semi-conductor, dyestuff with its preparation is usually used in the dyeing of cotton fibre with the Yin perylene, has good application fastness, pigment dyestuff with its preparation has excellent performance, it is the high-grade variety in the pigment dyestuff, big π-pi-conjugated system has been given its good fluorescence property and photoelectric properties in its molecular structure simultaneously, makes its derivative in fields such as xerox, solar cell, organic field effect tubes application be arranged all.Qi Shi perylene of You be one of organic semiconductor focus of having become people research now (CN02140158.6, CN200710012728.6).Why organic semiconductor comes into one's own, and is that it has following distinguishing feature because compare with traditional inorganic semiconductor:
1 organic molecule is of a great variety, and chemical structure is easy to change, and helps the design of material and device.
2. organic semiconductor is easy to the big area film forming, and is beneficial to extensive growth.
3. organic polymer can conduct electricity, again can be luminous, and it is integrated to be convenient to photoelectricity.
4. with low cost.
5. film-forming process is many, prepares easyly, can be prepared by chemical reaction.
6. can be made into the device of big area, full flexible.
3,4,9, the 10-3,4, 9, 10-perylenetetracarboxylic dianhydride has the solvability of non-constant in organic solvent, and the general bromination (DE19547209) in the vitriol oil earlier of the derivatize on the perylene ring is carried out the synthetic of various derivatives, severe reaction conditions again.
Bibliographical information in 2006 (Chem.Phys.Lett.2006,417:457) 3,4,9, synthesizing of 10-perylene tetramethyl acid esters, it has good solvability and big optical extinction coefficient, has liquid crystal behavior simultaneously, but does not see 3,4,9, the report of 10-perylene tetracarboxylic acid ester derivative.
Summary of the invention
The objective of the invention is to introduce on the Zai perylene bis diimines trifluoromethyl of different numbers, Yi Ti Gao perylene bis diimines compounds significantly improves its solvability in organic solvent simultaneously to the stability of light, heat and oxygenant.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of trifluoromethyl replaces the preparation method of De perylene bis diimines, adopts following preparation steps:
(1) bromine synthetic for perylene tetramethyl acid esters; is raw material with perylene tetramethyl acid esters and liquid bromine, their mass ratio equal 1: 4～and 100, be acid binding agent with salt of wormwood or yellow soda ash; the mass ratio of perylene tetramethyl acid esters and acid binding agent equals 1: 1～and 100, in first organic solvent, 0～80 ℃, stir down, reaction 1～72h; the hydrogen on the former material perylene tetramethyl acid esters is replaced by Br generates bromine for perylene tetramethyl acid esters, and its chemical molecular general structure is as follows:
In the formula: R
1～R
4=1～4 bromine atoms, R
5=C
1～C
30Straight chain, branched-chain alkyl.
(2) the perylene tetramethyl acid esters of the perylene tetramethyl acid esters of long-chain perfluoroalkyl replacement or trifluoromethyl replacement is synthetic, is raw material with bromine for perylene tetramethyl acid esters and perfluoroalkyl iodide, their mass ratio equals 1: 1～and 1000, with copper powder or gunmetal powder is catalyzer; bromine for the mass ratio of perylene tetramethyl acid esters and catalyzer equal 1: 1～100, in second organic solvent, 40～160 ℃, at Ar or N
2Gas shield and stirring are reacted 1～72h down, and the Br on the former material perylene ring is replaced by perfluoroalkyl, generate the perylene tetramethyl acid esters that perfluoroalkyl replaces, and its chemical molecular general structure is as follows:
In the formula: R
5=C
1～C
30Straight chain, branched-chain alkyl, R
6～R
9=1～4 long-chain perfluoroalkyls, the general structure of long-chain perfluoroalkyl are CF
3(CF
2) nCF
2-(even numbers of n=2～28);
Is raw material with bromine for perylene tetramethyl acid esters and sodium trifluoroacetate, and their mass ratio equals 1: 1～100, is catalyzer with the cuprous iodide, bromine for the mass ratio of perylene tetramethyl acid esters and catalyzer equal 1: 1～100, in second organic solvent, 40～160 ℃, at Ar or N
2Gas shield and stirring are reacted 1～72h down, and the Br on the former material perylene ring is replaced by trifluoromethyl, generate the perylene tetramethyl acid esters that trifluoromethyl replaces; Its chemical molecular general structure is as follows:
In the formula: R
5=C
1～C
30Straight chain, branched-chain alkyl, R
10～R
13=1～4 trifluoromethyls.
(3) perfluoroalkyl replaces the synthetic of De perylene tetracarboxylic acid Huo 3,4, 9, 10-perylenetetracarboxylic dianhydride, the perylene tetramethyl acid esters (the perylene tetramethyl acid esters that perylene tetramethyl acid esters that the long-chain perfluoroalkyl replaces or trifluoromethyl replace) that replaces with perfluoroalkyl is a raw material, the potassium hydroxide of 4～1000 times of raw materials quality or sodium hydroxide exist down, the perylene tetramethyl acid esters that perfluoroalkyl replaces and the mass ratio of potassium hydroxide or sodium hydroxide equal 1: 1～and 1000, at the aqueous solution of 10～95% alcohol or without mineral alkali, directly hydrolysis in chlorsulfonic acid, material concentration equals 1～1000mg/mL, 0～100 ℃, stir down, reaction 1～72h, acetate, propionic acid, hydrochloric acid or sulfuric acid acid acidifying, acid equals 1: 1 with the mass ratio of potassium hydroxide or sodium hydroxide～and 10, generate perfluoroalkyl and replace De perylene tetracarboxylic acid, its chemical molecular general structure is as follows:
In the formula: R
14～R
17=1～4 perfluoroalkyls, the general structure of perfluoroalkyl are CF
3(CF
2) nCF
2-(even numbers of n=2～28) or CF3-;
Perfluoroalkyl replacement De perylene tetracarboxylic acid dewaters easily and generates the following acid anhydride of chemical molecular general structure:
In the formula: R
14～R
17=1～4 perfluoroalkyls, the general structure of perfluoroalkyl are CF
3(CF
2) nCF
2-(even numbers of n=2～28) or CF3-.
(4) trifluoromethyl replaces the synthetic of De perylene bis diimines, replacing De 3,4, 9, 10-perylenetetracarboxylic dianhydride and alkylamine or aniline with trifluoromethyl is raw material, both mass ratioes are 1: 2～200, in the 3rd organic solvent, stir down, 20～150 ℃, reaction 1～24h, generate trifluoromethyl and replace the De perylene bis diimines, its chemical molecular general structure is as follows:
In the formula: R
18==C
1～C
18Straight chain, branched-chain alkyl, phenyl or hydrogen atom, R
19～R
22=1～4 trifluoromethyls.
Above described trifluoromethyl replace in the preparation of De perylene bis diimines, first organic solvent is selected from tetrahydrofuran (THF), 1,4-two oxa-s six rings, acetonitrile, N, dinethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, imidazoles, ethylene glycol monomethyl ether, glycol dimethyl ether, chlorobenzene, orthodichlorobenzene, methylene dichloride, trichloromethane, toluene or tetramethylene sulfone; Second organic solvent is selected from tetrahydrofuran (THF), 1,4-two oxa-s six rings, acetonitrile, N, dinethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, imidazoles, ethylene glycol monomethyl ether, glycol dimethyl ether or tetramethylene sulfone; Alcohol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, 1, ammediol, the trimethyl carbinol or glycerol; The 3rd organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, 1, ammediol, the trimethyl carbinol, glycerol, acetate, propionic acid or butyric acid.
After the invention has the beneficial effects as follows the trifluoromethyl of introducing different numbers on the: Zai perylene bis diimines, Ti Gao perylene bis diimines compounds significantly improves its solvability in organic solvent simultaneously to the stability of light, heat and oxygenant.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:1,7-two trifluoromethyls-N, the preparation of N '-Er Ding Ji perylene bis diimines
The synthetic route of this compound is seen last figure, and is synthetic by following four steps:
(1) 1,7-Er Xiu perylene tetracarboxylic acid four butyl esters and 1, synthesizing of 6-Er Xiu perylene tetracarboxylic acid four butyl ester mixtures adds 820mg perylene tetracarboxylic acid four butyl esters (1.24mmol), 306mg K in the 100mL two-mouth bottle
2CO
3(2.2mmol), 60mL CH
2Cl
2, add 4mL liquid bromine (78.4mmol), stir down, 10 ℃ of maintenance systems, reaction 2h crosses silicagel column, gets 1,7-Er Xiu perylene tetracarboxylic acid four butyl esters and 1,6-Er Xiu perylene tetracarboxylic acid four butyl ester mixture 600mg, yield 60%, API-ES-MS, [M+Na]
+: 831 (m/z);
1H-NMR (400Mz, CDCl3): δ=0.85-1.85 (m, 28H), 4.35 (m, 8H), 8.03 (m, 2H ， perylene rings), 8.31 (m, 2H ， perylene rings), 8.83 (m, 2H ， perylene rings);
13C-NMR (100MHz, CDCl
3): δ=14.0,19.4,65.8,66.0,118.8,126.6,127.7,129.2,130.5,130.6,131.2,131.8,131.9,136.8,167.3,168.1;
Synthesizing of (2) 1,7-two San Fu Jia Ji perylene tetracarboxylic acids four butyl esters, add 320mg 1 in the 20mL flask; 7-Er Xiu perylene tetracarboxylic acid four butyl esters and 1, the mixture (0.4mmol) of 6-Er Xiu perylene tetracarboxylic acid four butyl esters, 5.48g sodium trifluoroacetate (40mmol); 1.52g cuprous iodide (8mmol), 12mL DMF, the Ar protection is down; back flow reaction 10h crosses silicagel column, gets 1; 7-two San Fu Jia Ji perylene tetracarboxylic acids four butyl ester 204mg; yield 66%, API-ES-MS, [M]
-: 788 (m/z);
1H-NMR (400Mz, CDCl
3): δ=0.85-1.85 (m, 28H), 4.23 (m, 8H), 8.55 (d, 2H ， perylene rings), 8.79 (d, 2H ， perylene rings), 9.06 (s, 2H ， perylene rings);
19F-NMR (376.5MHz, CDCl
3): δ=-55.2;
The preparation of (3) 1,7-two San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides adds 200mg 1,7-two San Fu Jia Ji perylene tetracarboxylic acid four butyl esters (0.25mmol) in the 5mL flask, 2.5mL chlorsulfonic acid stirs following 30 ℃ of reaction 4h, gets 1,7-two San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 124mg, yield 94%, APCI-MS, [M]
-: 528 (m/z);
1H-NMR (400Mz, CF
3COOD): 8.91 (d, 2H ， perylene rings), 9.01 (d, 2H ， perylene rings), 9.27 (s, 2H ， perylene rings);
The preparation of (4) 1,7-two San Fu Jia Ji perylene bis diimines adds 105mg 1 in the 10mL flask; 7-two San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides (0.2mmol); 1.46g n-Butyl Amine 99 (20mmol), 4mL ethanol, the Ar protection is down; back flow reaction 1h; get 1,7-two San Fu Jia Ji perylene bis diimines 120mg, yield 94%; APCI-MS, [M]
-: 638 (m/z);
1H-NMR (400Mz, CDCl
3): δ=0.85-1.85 (m, 14H), 4.23 (m, 4H), 8.55 (d, 2H ， perylene rings), 8.79 (d, 2H ， perylene rings), 9.06 (s, 2H ， perylene rings);
19F-NMR (376.5MHz, CDCl3): δ=-55.8.
In the four-step reaction of perylene bis diimines preparation, per step reaction all is independently, can change reaction conditions or raw material, and embodiment 2～27 will specify.
The following examples 2～5 are the preparation of bromine for perylene tetramethyl acid esters.
The preparation of embodiment 2:1-Xiu perylene tetracarboxylic acid four butyl esters
Add 3.0g perylene tetracarboxylic acid four butyl esters (4.6mmol) in the 100mL two-mouth bottle, 3.0g K
2CO
3(22mmol), 50mL CH2Cl2 adds 3mL liquid bromine (59mmol), stir down, and 20 ℃ of maintenance systems, reaction 1.5h crosses silicagel column, gets 1-Xiu perylene tetracarboxylic acid four butyl ester 900mg, yield 27%, API-ES-MS, [M+Na]
+: 753 (m/z);
1H-NMR (400Mz, CDCl3): δ=0.85-1.85 (m, 28H), 4.36 (m, 8H), 7.97 (d, 1H ， perylene rings), 8.02 (d, 2H ， perylene rings), 8.10 (m, 2H ， perylene rings), 8.26 (s, 1H ， perylene rings), 8.98 (d, 1H ， perylene rings);
13C-NMR (100MHz, CDCl
3): δ=13.8,19.2,19.3,30.6,65.4,65.5,65.7,118.6,121.6,122.6,127.3,128.0,129.2,129.5,130.0,130.1,130.2,130.4,130.8,130.9,131.6,132.1,132.4,132.5,137.4.
Embodiment 3:1,6,7-San Xiu perylene tetracarboxylic acid four butyl esters and 1,6,7, the preparation of 12-Si Xiu perylene tetracarboxylic acid four butyl esters
Add 410mg perylene tetracarboxylic acid four butyl esters (0.62mmol) in the 25mL two-mouth bottle, 552mg K
2CO
3(4mmol), the 15mL chlorobenzene adds 1mL liquid bromine (19.6mmol), stir down, and 80 ℃ of maintenance systems, reaction 48h crosses silicagel column, gets 1,6,7-San Xiu perylene tetracarboxylic acid four butyl ester 110mg, yield 19%API-ES-MS, [M+Na]
+: 908 (m/z) and 1,6,7,12-Si Xiu perylene tetracarboxylic acid four butyl ester 300mg, yield 50%, API-ES-MS, [M+Na]
+: 986 (m/z).
The preparation of embodiment 4:1-Xiu perylene tetracarboxylic acid four octadecyl esters
Add 1.4g perylene tetracarboxylic acid four octadecyl esters (1mmol) in the 25mL two-mouth bottle, 106g Na
2CO
3(1mmol), 15mL CHCl
3, add 0.1mL liquid bromine (2mmol), stir down, 60 ℃ of maintenance systems, reaction 72h crosses silicagel column, gets 1-Xiu perylene tetracarboxylic acid four octadecyl ester 1.3g, yield 84%, API-ES-MS, [M+Na]
+: 1538 (m/z).
Embodiment 5:1,6,7, the preparation of 12-Si Xiu perylene tetracarboxylic acid four different monooctyl esters
Add 880mg perylene tetracarboxylic acid four different monooctyl esters (1mmol) in the 25mL two-mouth bottle, 2.7g K
2CO
3(20mmol), the 15mL chlorobenzene adds 5mL liquid bromine (98mmol), stir down, and 60 ℃ of maintenance systems, reaction 48h crosses silicagel column, gets 1,6,7,12-Si Xiu perylene tetracarboxylic acid four different monooctyl ester 1.1g, yield 92%, API-ES-MS, [M+Na]
+: 1211 (m/z).
The following examples 6～13 are the preparation of the perylene tetramethyl acid esters of long-chain perfluoroalkyl or trifluoromethyl replacement.
The preparation of embodiment 6:1-full fluorine Ji Ji perylene tetracarboxylic acid four butyl esters
Add 730mg 1-Xiu perylene tetracarboxylic acid four butyl esters (1mmol) in the 10mL flask; 640mg copper powder (10mmol), 5mL dimethyl sulfoxide (DMSO), 400 μ L (1.8mmol) iodo perfluoro hexanes; the Ar protection down; 100 ℃ of maintenance systems, reaction 12h crosses silicagel column; get 1-full fluorine Ji Ji perylene tetracarboxylic acid four butyl ester 710mg; yield 73%, API-ES-MS, [M+Na]
+: 993 (m/z).
The preparation of embodiment 7:1-full fluorine Xin Ji perylene tetracarboxylic acid four butyl esters
Add 150mg 1-Xiu perylene tetracarboxylic acid four butyl esters (0.2mmol) in the 5mL flask; 64mg copper powder (1mmol), 2mL dimethyl sulfoxide (DMSO), 200 μ L (0.73mmol) iodo perfluoro octanes; the Ar protection down; 100 ℃ of maintenance systems, reaction 12h crosses silicagel column; get 1-full fluorine Xin Ji perylene tetracarboxylic acid four butyl ester 112mg; yield 50%, API-ES-MS, [M+Na]
+: 1093 (m/z); 1H-NMR (400Mz, CDCl3): δ=0.85-1.85 (m, 28H), 4.36 (m, 8H), 7.94 (d, 1H ， perylene rings), 8.03 (d, 1H ， perylene rings), 8.16 (d, 1H ， perylene rings), 8.21 (d, 1H ， perylene rings), 8.33 (m, 2H ， perylene rings), 8.40 (s, 1H ， perylene rings);
19F-NMR (376.5MHz, CDCl3): δ=-126.0 ,-122.6 ,-121.8 ,-121.5 ,-121.0 ,-97.4 ,-80.8.
Embodiment 8:1,7-two full fluorine Xin Ji perylene tetracarboxylic acid four butyl esters and 1, the preparation of 6-two full fluorine Xin Ji perylene tetracarboxylic acids four butyl esters
Add 800mg 1 in the 10mL flask; 7-Er Xiu perylene tetracarboxylic acid four butyl esters and 1, the mixture of 6-Er Xiu perylene tetracarboxylic acid four butyl esters (is made by embodiment 2,1mmol); 800mg copper powder (12.5mmol); 5mL N, dinethylformamide, 1.5mL (5.5mmol) iodo perfluoro octane; the Ar protection down; 100 ℃ of maintenance systems, reaction 12h crosses silicagel column; obtain 1; 7-two full fluorine Xin Ji perylene tetracarboxylic acid four butyl esters and 1,6-two full fluorine Xin Ji perylene tetracarboxylic acids four butyl esters, wherein 1; 7-two full fluorine Xin Ji perylene tetracarboxylic acids four butyl ester 600mg; yield 40%, API-ES-MS, [M+Na]
+: 1093 (m/z);
1H-NMR (400Mz, CDCl
3): δ=0.85-1.85 (m, 28H), 4.39 (m, 8H), 7.92 (m, 2H ， perylene rings), 8.14 (d, 2H ， perylene rings), 8.38 (s, 2H ， perylene rings);
19F-NMR (376.5MHz, CDCl
3): δ=-126.1 ,-122.7 ,-121.8 ,-121.6 ,-121.0 ,-116.6 ,-97.5 ,-80.9; 1,6-two full fluorine Xin Ji perylene tetracarboxylic acids four butyl ester 110mg, yield 7.4%, API-ES-MS, [M+Na]
+: 1093 (m/z);
1H-NMR (400Mz, CDCl
3): δ=0.85-1.85 (m, 28H), 4.39 (m, 8H), 8.06 (m, 2H ， perylene rings), 8.09 (d, 2H ， perylene rings), 8.51 (s, 2H ， perylene rings);
19F-NMR (376.5MHz, CDCl3): δ=-126.5 ,-123.1 ,-122.2 ,-122.0 ,-121.5 ,-115.8 ,-97.5 ,-81.2.
Embodiment 9:1,6, the preparation of 7-three full fluorine Xin Ji perylene tetracarboxylic acids four butyl esters
Add 87.5mg 1,6 in the 5mL flask, 7-Er Xiu perylene tetracarboxylic acid four butyl esters (0.1mmol); 100mg gunmetal powder (90wt%Cu, 1.4mmol), 2mL N; dinethylformamide, 400 μ L (1.5mmol) iodo perfluoro octanes, the Ar protection is down; 100 ℃ of maintenance systems, reaction 10h crosses silicagel column; obtain 1,6,7-three full fluorine Xin Ji perylene tetracarboxylic acids four butyl ester 82mg; yield 43%, API-ES-MS, [M+Na]
+: 1915 (m/z).
Embodiment 10:1,6,7, the preparation of 12-four full fluorine Xin Ji perylene tetracarboxylic acids four different monooctyl esters
Add 119mg 1,6,7 in the 5mL flask, 12-Si Xiu perylene tetracarboxylic acid four butyl esters (0.1mmol); 200mg gunmetal powder (90wt%Cu, 2.8mmol), 2mL N, dinethylformamide; 800 μ L (3mmol) iodo perfluoro octanes, under the Ar protection, 70 ℃ of maintenance systems; reaction 72h crosses silicagel column, obtains 1; 6,7,12-four full fluorine Xin Ji perylene tetracarboxylic acids four different monooctyl ester 70mg; yield 27%, API-ES-MS, [M+Na]
+: 2571 (m/z).
The preparation of embodiment 11:1-full fluorine Xin Ji perylene tetracarboxylic acid four octadecyl esters
Add 152mg 1-Xiu perylene tetracarboxylic acid four butyl esters (0.1mmol) in the 5mL flask; 64mg copper powder (1mmol), 2mL dimethyl sulfoxide (DMSO), 200 μ L (0.73mmol) iodo perfluoro octanes; the Ar protection down; 100 ℃ of maintenance systems, reaction 12h crosses silicagel column; get 1-full fluorine Xin Ji perylene tetracarboxylic acid four butyl ester 100mg; yield 54%, API-ES-MS, [M+Na]
+: 1878 (m/z).
The preparation of embodiment 12:1-San Fu Jia Ji perylene tetracarboxylic acid four butyl esters
Add 73mg 1-Xiu perylene tetracarboxylic acid four butyl esters (0.1mmol) in the 5mL flask, 137mg sodium trifluoroacetate (1mmol), 190mg cuprous iodide (1mmol), 2mL DMF; under the Ar protection, back flow reaction 1h crosses silicagel column, gets 1-San Fu Jia Ji perylene tetracarboxylic acid four butyl ester 51mg; yield 71%, APCI-MS, [M]
-: 720 (m/z).
Embodiment 13:1,6,7, the preparation of 12-four San Fu Jia Ji perylene tetracarboxylic acids four butyl esters
Add 97mg 1,6 in the 10mL flask, 7; 12-Si Xiu perylene tetracarboxylic acid four butyl esters (0.1mmol), 1.37g sodium trifluoroacetate (10mmol), 1.9g cuprous iodide (10mmol); 5mL DMF, under the Ar protection, back flow reaction 10h; cross silicagel column, get 1,6; 7,12-four San Fu Jia Ji perylene tetracarboxylic acids four butyl ester 38mg, yield 41%; APCI-MS, [M]
-: 924.
The perylene tetramethyl acid esters that the following examples 14～23 perfluoroalkyls replace or the preparation of 3,4, 9, 10-perylenetetracarboxylic dianhydride.
The preparation of embodiment 14:1-full fluorine Ji Ji perylene tetracarboxylic acid
Add 970mg 1-full fluorine Ji Ji perylene tetracarboxylic acid four butyl esters (1mmol) in the 25mL flask, the 15mL trimethyl carbinol, 1.5mL water, 0 ℃ of 5.6g KOH (100mmol), reaction 12h, the acidifying of 120mmol acetate gets 1-full fluorine Ji Ji perylene tetracarboxylic acid 740mg, yield 99%, API-ES-MS, [M+Cl]
-: 781 (m/z).
The preparation of embodiment 15:1-full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride
Add 107mg 1-full fluorine Xin Ji perylene tetracarboxylic acid four butyl esters (0.1mmol) in the 5mL flask, the 2mL trimethyl carbinol, 0.5mL water, 400g KOH (7.1mmol) stirs back flow reaction 5h down, 7.1mmol acetate acidifying, filter recrystallization in the propionic acid of back, get 1-full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 73mg, yield 90%, API-ES-MS, [M+Cl]
-: 836 (m/z);
1H-NMR (400Mz, CF3COOD): 8.45 (s, 1H ， perylene rings), 8.61 (d, 1H ， perylene rings), 8.70 (d, 3H ， perylene rings), 8.76 (d, 1H ， perylene rings), 8.90 (s, 1H ， perylene rings);
19F-NMR (376.5MHz, CDCl3): δ=-126.3 ,-122.9 ,-122.0 ,-121.7 ,-121.3 ,-97.9 ,-81.1.
Embodiment 16:1, the preparation of 7-two full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides
Add 149mg 1 in the 10mL flask, 7-two full fluorine Xin Ji perylene tetracarboxylic acid four butyl esters (0.1mmol), the 6mL trimethyl carbinol, 1mL water, 400mg NaOH (10mmol) stirs back flow reaction 5h down, the acidifying of 100mmol propionic acid, filter recrystallization in the propionic acid of back, get 1,7-two full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 110mg, yield 89%, API-ES-MS, [M+Cl]
-: 1263 (m/z);
1H-NMR (400Mz, CF
3COOD): 8.37 (m, 2H ， perylene rings), 8.68 (d, 2H ， perylene rings), 8.94 (s, 2H ， perylene rings);
19F-NMR (376.5MHz, CDCl
3): δ=-126.5 ,-123.1 ,-122.2 ,-122.0 ,-121.5 ,-116.2 ,-98.2 ,-81.1.
Embodiment 17:1, the preparation of 6-two full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides
Add 149mg1 in the 250mL flask, 6-two full fluorine Xin Ji perylene tetracarboxylic acid four butyl esters (0.1mmol), 100mL ethanol, 10mL water, 4g NaOH (100mmol) stirs back flow reaction 72h down, the 110mmol hcl acidifying, filter recrystallization in the propionic acid of back, get 1,6-two full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 105mg, yield 85%, API-ES-MS, [M+Cl]
-: 1263 (m/z).
The preparation of embodiment 18:1-full fluorine Ji Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride
Add 97mg 1-full fluorine Ji Ji perylene tetracarboxylic acid four butyl esters (0.1mmol) in the 5mL flask, the 2mL trimethyl carbinol, 1mL water, 400mg KOH (7.1mmol) stirs back flow reaction 5h down, the 8mmol sulfuric acid acidation, filter recrystallization in the propionic acid of back, get 1-full fluorine Ji Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 50mg, yield 70%, API-ES-MS, [M+Cl]
-: 745 (m/z).
Embodiment 19:1,6, the preparation of 7-three full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides
Add 1.9g 1,6 in the 5mL flask, 7-three full fluorine Xin Ji perylene tetracarboxylic acid four butyl esters (1mmol), the 2mL chlorsulfonic acid stirs following 0 ℃ of reaction 10h, gets 1,6,7-three full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 1.6g, yield 97%, API-ES-MS, [M+Cl]
-: 1681 (m/z);
Embodiment 20:1,6,7, the preparation of 12-four full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides
Add 255mg 1,6,7 in the 5mL flask, the 12-four full fluorine Xin Ji different monooctyl esters of perylene tetracarboxylic acid (0.1mmol), the 2mL chlorsulfonic acid stirs following 60 ℃ of reaction 10h, gets 1,6,7,12-four full fluorine Xin Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 180mg, yield 87%, API-ES-MS, [M+Cl]
-: 2098 (m/z).
The preparation of embodiment 21:1-San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride
Add 144mg 1-San Fu Jia Ji perylene tetracarboxylic acid four butyl esters (0.2mmol) in the 5mL flask, the 2mL chlorsulfonic acid stirs following 0 ℃ of reaction 10h, gets 1-San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 85mg, yield 92%, APCI-MS, [M]
-: 460 (m/z).
Embodiment 22:1, the preparation of 7-two San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides
Add 158mg 1 in the 5mL flask, 7-two San Fu Jia Ji perylene tetracarboxylic acid four butyl esters (0.2mmol), the 2mL chlorsulfonic acid stirs down, and 30 ℃ of reaction 4h get 1,7-two San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 98mg, yield 94%, APCI-MS, [M]
-: 528 (m/z);
1H-NMR (400Mz, CF
3COOD): 8.91 (d, 2H ， perylene rings), 9.01 (d, 2H ， perylene rings), 9.27 (s, 2H ， perylene rings).
Embodiment 23:1,6,7, the preparation of 12-four San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides
Add 184mg 1,6 in the 5mL flask, 7,12-four San Fu Jia Ji perylene tetracarboxylic acid four butyl esters (0.2mmol), the 2mL trimethyl carbinol, 1mL water, 400mg KOH (7.1mmol) stirs back flow reaction 4h down, the 8mmol sulfuric acid acidation, filter recrystallization in the propionic acid of back, get 1,6,7,12-four San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride 100mg, yield 72%, APCI-MS, [M]
-: 664 (m/z).
The following examples 24～27 replace the preparation of De perylene bis diimines for trifluoromethyl.
The preparation of embodiment 24:1-San Fu Jia Ji perylene bis diimines
Add 92mg 1-San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydride (0.2mmol) in the 5mL flask, 190mg ammonium acetate (2mmol), 3mL acetate, under the Ar protection, back flow reaction 10h gets 1-San Fu Jia Ji perylene bis diimines 90mg, yield 98%, APCI-MS, [M]
-: 458 (m/z).
Embodiment 25:1,7-two trifluoromethyls-N, the preparation of N '-Er Xin Ji perylene bis diimines
Add 105mg 1 in the 10mL flask, 7-two San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides (0.2mmol), 1.46g n-Butyl Amine 99 (20mmol), 4mL ethanol; under the Ar protection, back flow reaction 1h gets 1,7-two trifluoromethyls-N; N '-Er Xin Ji perylene bis diimines 120mg, yield 94%, APCI-MS, [M]
-: 750 (m/z);
1H-NMR (400Mz, CDCl
3): δ=0.85-1.85 (m, 30H), 4.21 (m, 4H), 8.54 (d, 2H ， perylene rings), 8.78 (d, 2H ， perylene rings), 9.05 (s, 2H ， perylene rings); 19F-NMR (376.5MHz, CDCl
3): δ=-55.8.
Embodiment 26:1,6,7,12-four trifluoromethyls-N, the preparation of N '-two Shi Ba Wan Ji perylene bis diimines
Add 133mg 1,6 in the 10mL flask, 7; 12-four San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides (0.2mmol), 129g n-octyl amine (1mmol), 5mL propionic acid; under the Ar protection, 140 ℃ of reaction 24h get 1; 6,7,12-four trifluoromethyls-N; N '-two Shi Ba Wan Ji perylene bis diimines 210mg; yield 90%, APCI-MS, [M]
-: 1166 (m/z).
Embodiment 27:1,7-two trifluoromethyls-N, the preparation of N '-Er Ben Ji perylene bis diimines
Add 105mg 1 in the 10mL flask, 7-two San Fu Jia Ji 3,4, 9, 10-perylenetetracarboxylic dianhydrides (0.2mmol), 19mg aniline (0.4mmol), 4mL acetate; under the Ar protection, 20 ℃ of reaction 24h get 1,7-two trifluoromethyls-N; N '-Er Ben Ji perylene bis diimines 130mg, yield 96%, APCI-MS, [M]
-: 678 (m/z).
Claims (5)
1. the preparation method of the perylene bis diimines that replaces of a trifluoromethyl is characterized in that: adopt following preparation steps:
(1) bromine synthetic for perylene tetramethyl acid esters; is raw material with perylene tetramethyl acid esters and liquid bromine, their mass ratio equal 1: 4～and 100, be acid binding agent with salt of wormwood or yellow soda ash; the mass ratio of perylene tetramethyl acid esters and acid binding agent equals 1: 1～and 100, in first organic solvent, 0～80 ℃, stir down, reaction 1～72h; the hydrogen on the former material perylene tetramethyl acid esters is replaced by Br generates bromine for perylene tetramethyl acid esters, and its chemical molecular general structure is as follows:
In the formula: R
1～R
4Be bromine, R
5Be C
1～C
30Straight chain, branched-chain alkyl;
(2) the perylene tetramethyl acid esters of trifluoromethyl replacement is synthetic, is raw material with bromine for perylene tetramethyl acid esters and sodium trifluoroacetate, their mass ratio equals 1: 1～and 100, with the cuprous iodide is catalyzer; bromine for the mass ratio of perylene tetramethyl acid esters and catalyzer equal 1: 1～100, in second organic solvent, 40～160 ℃, at Ar or N
2Gas shield and stirring are reacted 1～72h down, and the Br on the former material perylene ring is replaced by trifluoromethyl, generate the perylene tetramethyl acid esters that trifluoromethyl replaces; Its chemical molecular general structure is as follows:
In the formula: R
5Be C
1～C
30Straight chain, branched-chain alkyl, R
10～R
13Be trifluoromethyl;
(synthesizing of 3) 3,4, 9, 10-perylenetetracarboxylic dianhydrides, the perylene tetramethyl acid esters that replaces with trifluoromethyl is a raw material, the potassium hydroxide of 4～1000 times of raw materials quality or sodium hydroxide exist down, at the aqueous solution of 10～95% alcohol or without mineral alkali, directly hydrolysis in chlorsulfonic acid, material concentration equals 1～1000mg/mL, 0～100 ℃, stir down, reaction 1～72h, acetate, propionic acid, hydrochloric acid or sulfuric acid acidation, acid equal 1: 1 with the mass ratio of potassium hydroxide or sodium hydroxide～and 10, generate trifluoromethyl and replace De perylene tetracarboxylic acid;
Trifluoromethyl replacement De perylene tetracarboxylic acid dewaters easily and generates the following acid anhydride of chemical molecular general structure:
In the formula; R
14～R
17Be trifluoromethyl;
(4) trifluoromethyl replaces the synthetic of De perylene bis diimines, replacing De 3,4, 9, 10-perylenetetracarboxylic dianhydride and alkylamine or aniline with trifluoromethyl is raw material, both mass ratioes are 1: 2～200, in the 3rd organic solvent, stir down, 20～150 ℃, reaction 1～24h, generate trifluoromethyl and replace the De perylene bis diimines, its chemical molecular general structure is as follows:
In the formula: R
18Be C
1～C
18Straight chain, branched-chain alkyl or phenyl, R
19～R
22Be trifluoromethyl.
2. the preparation method who replaces the De perylene bis diimines according to the described trifluoromethyl of claim 1, it is characterized in that: described first organic solvent is selected from tetrahydrofuran (THF), 1,4-two oxa-s six rings, acetonitrile, N, dinethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, imidazoles, ethylene glycol monomethyl ether, glycol dimethyl ether, chlorobenzene, orthodichlorobenzene, methylene dichloride, trichloromethane, toluene or tetramethylene sulfone.
3. the preparation method who replaces the De perylene bis diimines according to the described trifluoromethyl of claim 1, it is characterized in that: second organic solvent is selected from tetrahydrofuran (THF), 1,4-two oxa-s six rings, acetonitrile, N, dinethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, quinoline, imidazoles, ethylene glycol monomethyl ether, glycol dimethyl ether or tetramethylene sulfone.
4. replace the preparation method of De perylene bis diimines according to the described trifluoromethyl of claim 1, it is characterized in that: described alcohol is selected from methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, 1, ammediol, the trimethyl carbinol or glycerol.
5. the preparation method who replaces the De perylene bis diimines according to the described trifluoromethyl of claim 1, it is characterized in that: described the 3rd organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, 1, ammediol, the trimethyl carbinol, glycerol, acetate, propionic acid or butyric acid.
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| CN103965093A (en) * | 2014-04-04 | 2014-08-06 | 华南理工大学 | 2-perfluoroalkyl indole compound as well as preparation and application thereof |
| CN104098432B (en) * | 2014-06-30 | 2016-03-30 | 福建师范大学福清分校 | A kind of synthetic method of trifluoromethylation aromatic hydrocarbons |
| CN107602391A (en) * | 2017-07-20 | 2018-01-19 | 南京邮电大学 | Intelligent control circular polarization fluorescent derivative photoelectric material preparation method |
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