CN105061135A - Method for synthesis of hexa-cata-hexabenzocoronene and derivatives thereof - Google Patents
Method for synthesis of hexa-cata-hexabenzocoronene and derivatives thereof Download PDFInfo
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Abstract
The invention discloses a method for synthesis of hexa-cata-hexabenzocoronene and derivatives thereof. The method comprises the steps: with 2-bromobenzoyl chloride as a raw material, carrying out a friedel-crafts acylation reaction and a boronation reaction with benzene or a substituent benzene to obtain 2-benzoyl benzeneboronic acid pinacol ester and derivatives thereof, further, carrying out a Suzuki coupling reaction with 1,3,5-tris(bromomethyl)benzene to construct a c-HBC skeleton-1,3,5-tris(((2-benzoyl)phenyl)methyl)benzene and derivatives thereof, and then successively carrying out a reduction reaction, a friedel-crafts reaction and a Scholl cyclization reaction to synthesize the hexa-cata-hexabenzocoronene and the derivatives thereof. The method is mild in reaction conditions and convenient to operate, enables the highest total yield of the products to reach more than or equal to 80%, and can be used for mass production; the synthesized hexa-cata-hexabenzocoronene and the derivatives thereof have no need of alkoxy as a guidance group and a positioning group; and the method is a simple and convenient method for synthesis of the hexa-cata-hexabenzocoronene and the derivatives thereof.
Description
Technical field
The invention belongs to the synthesis technical field of polycyclic aromatic hydrocarbon compounds, be specifically related to the synthetic method of a kind of six vast Liu Ben Bing guan (hexa-cata-hexabenzocoronene, c-HBC) compounds and derivative thereof.
Background technology
The fragrant core of c-HBC and derivative thereof is distortion, and the distortion carbon atom of its planar central carbon atom near-end departs from 20 °, plane because space is crowded, structurally in concave-concave conformation, and compound that can be special with some, such as C
60, form the complex compound of geometry complementation.C-HBC also has the structural unit of linear acene (linearacenes) simultaneously, and this linear acene is well-known electronic material.In addition, the disk-like structure of c-HBC makes it become a kind of potential column liquid crystal core, have good electron-transporting and good photoluminescence effect, in scene effect transistor, organic semiconductor material, photovoltaic cell and photorectifier, there is potential widespread use.
Clar study group is in the nineteen sixty-five reported first synthesis of c-HBC (Tetrahedron1965,21,467-470).They have first prepared the framework of a kind of tetraalkoxide compound as target molecule, then are mixed with copper powder by this compound, and at 400 DEG C, reaction can obtain c-HBC, obtains product through column chromatography for separation, yield only about 2%.The acquisition methods of the c-HBC of current report and the best of derivative thereof has two kinds, a kind of be Nuckolls study group development with pentacene quinone for raw material, react through double Barton-Kelloggolefination, or carry out the Suzuki linked reaction of quadruple with fragrant boric acid, close ring further by Sholl and obtain c-HBC and mirror symmetry derivative (Angew.Chem.Int.Ed.2005 thereof, 44,7390-7394; Org.Lett., 2009,11:2225-2228; Chem.Sci., 2011,2,1480-1486).But the method is raw materials used not easily to be obtained, and expensive, is difficult to a large amount of production, the synthesis of the c-HBC derivative of different symmetry requirement cannot be met simultaneously.Another kind method is the synthetic method (J.Am.Chem.Soc., 2014,136:5057-5064) that 2014 Nian Weijunfa study group report a kind of c-HBC and derivative thereof.The method is with 1,3,5-(trisbromomethyl) benzene is raw material, obtain containing orientating group and 1 of the base that leads with electron rich virtue boric acid through triple Suzuki linked reactions, the center framework of 3,5-tri-(3,4-dialkoxy benzyl) benzene, and then with aromatic aldehyde, Fu Ke-aromizing-dehydrocyclization occurs and react, obtain three-fold symmetry c-HBC derivative.The intermediate of the method needs activating group alkoxyl group as guiding base, then cannot realize for simple c-HBC with without the synthesis of activation base as the c-HBC derivative of guiding base.
Summary of the invention
Technical problem solved by the invention is the shortcoming overcoming above-mentioned six vast Liu Ben Bing guans and derivative synthesizing process thereof, a kind of cheaper starting materials is provided to be easy to get, synthesis step is simple and direct, low in the pollution of the environment, mild condition, can produce in a large number and yield is high, without the need to alkoxyl group as guiding six vast Liu Ben Bing guans of base and the synthetic method of derivative thereof.
The synthetic route solving the problems of the technologies described above the technical scheme of employing is as follows:
In above-mentioned formula 1 ~ formula 6 compound, R
1, R
2, R
3, R
4independently represent separately in H, alkyl, alkoxyl group, phenyl, alkyl-substituted phenyl, alkoxy substituted phenyl any one, preferred R
1, R
2, R
3, R
4independently represent H, C separately
1~ C
4alkyl, C
1~ C
4any one in alkoxyl group, phenyl, further preferred R
1, R
2, R
3, R
4independently represent separately in H, methyl, methoxyl group, phenyl any one.
Concrete synthetic method is made up of following step:
1, friedel-crafts acylation
Adjacent bromo-benzoyl chloride is dissolved in methylene dichloride completely; 0 DEG C, add aluminum chloride and formula 1 compound under argon shield; the mol ratio of adjacent bromo-benzoyl chloride and aluminum chloride, formula 1 compound is 1:1 ~ 1.5:1 ~ 1.5; 0 DEG C or stirring at normal temperature reaction 2 ~ 3 hours; react with saturated ammonium chloride cancellation; separation and purification product, obtains formula 2 compound.
2, boronation reaction
With 1; 4-dioxane is solvent; under argon shield; by formula 2 compound, connection pinacol borate, Potassium ethanoate, [1; two (diphenylphosphino) ferrocene of 1'-] palladium chloride is 1:1.0 ~ 2.0:1.5 ~ 2.5:0.03 ~ 0.1 in molar ratio; 80 ~ 100 DEG C of stirring reactions 12 ~ 24 hours, separation and purification product, obtains formula 3 compound.
3, linked reaction
With 1; 4-dioxane is solvent; under argon shield; by 1; 3,5-(trisbromomethyl) benzene, formula 3 compound, salt of wormwood, tetrakis triphenylphosphine palladium are 1:3 ~ 5:4 ~ 6:0.03 ~ 0.1 in molar ratio, 80 ~ 100 DEG C of stirring reactions 12 ~ 24 hours; separation and purification product, obtains formula 4 compound.
4, reduction reaction
Taking methylene dichloride as solvent, is 1:12 ~ 20:12 ~ 20 by formula 4 compound, methyl alcohol, sodium borohydride in molar ratio, and normal-temperature reaction 1 ~ 2 hour, separation and purification product, obtains formula 5 compound.
5, ring closure reaction
Formula 5 compound is dissolved in methylene dichloride completely, add trifluoroacetic anhydride and trifluoromethanesulfonic acid, stirring at normal temperature 24 ~ 48 hours, then at 0 DEG C, the nitromethane solution of FERRIC CHLORIDE ANHYDROUS is dripped under argon shield, DDQ is added after dripping, formula 5 compound and trifluoroacetic anhydride, trifluoromethanesulfonic acid, FERRIC CHLORIDE ANHYDROUS, the mol ratio of DDQ is 1:7 ~ 10:0.5 ~ 1.0:2 ~ 3:5 ~ 7, 0 DEG C or stirring at normal temperature 30 ~ 120 minutes, add methyl alcohol cancellation reaction, separation and purification product, prepare six vast position six benzene shown in an accepted way of doing sth 6 and guan or derivatives thereof.
In above-mentioned steps 1, the mol ratio of preferred adjacent bromo-benzoyl chloride and aluminum chloride, formula 1 compound is 1:1:1.1.
In above-mentioned steps 2, preferred formula 2 compound is 1:1.5:2:0.05 with the mol ratio of connection pinacol borate, Potassium ethanoate, [two (diphenylphosphino) ferrocene of 1,1'-] palladium chloride.
In above-mentioned steps 3, preferably the mol ratio of 1,3,5-(trisbromomethyl) benzene and formula 3 compound, salt of wormwood, tetrakis triphenylphosphine palladium is 1:4.5:5:0.05.
In above-mentioned steps 4, the mol ratio of preferred formula 4 compound and methyl alcohol, sodium borohydride is 1:18:18.
In above-mentioned steps 5, the mol ratio of preferred formula 5 compound and trifluoroacetic anhydride, trifluoromethanesulfonic acid, FERRIC CHLORIDE ANHYDROUS, DDQ is 1:9:0.9:2.4:6.
Reaction conditions of the present invention is gentle, easy to operate, product total recovery reaches as high as more than 80%, can produce in a large number, six vast synthesized Liu Ben Bing guan derivatives as guiding base and orientating group, are a kind of method of easy synthesis six vast Liu Ben Bing guans and derivative thereof without the need to alkoxyl group.
Embodiment
Below in conjunction with embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiments.
Embodiment 1
For six vast Liu Ben Bing guans that composite structure formula is following, concrete synthetic method is as follows:
1, friedel-crafts acylation
The methylene dichloride of 2.19g (10mmol) adjacent bromo-benzoyl chloride and 50mL drying is added in 100mL there-necked flask, at 0 DEG C, under argon shield, add 1.33g (10mmol) aluminum chloride and 8.59g (11mmol) benzene, stirring at normal temperature reacts 3 hours, react with saturated ammonium chloride cancellation, with dichloromethane extraction three times, merge organic phase, with anhydrous sodium sulfate drying, rotary evaporation is except desolventizing, the mixed solution being 10:1 with the volume ratio of sherwood oil and ethyl acetate is for developping agent column chromatography separated product, obtain the 2-bromine benzophenone that structural formula is following, its productive rate is 98.2%.
2, boronation reaction
1.30g (5mmol) 2-bromine benzophenone is added successively in 50mL there-necked flask, 1.90g (7.5mmol) joins boric acid pinacol ester, 0.98g (10mmol) Potassium ethanoate, 0.18g (0.25mmol) [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride, 1 of 25mL drying, 4-dioxane, under argon shield, 100 DEG C of stirring reactions 24 hours, be chilled to room temperature, add distilled water diluting 2 times, be extracted with ethyl acetate three times, merge organic phase, with anhydrous sodium sulfate drying, rotary evaporation is except desolventizing, the mixed solution being 20:1 with sherwood oil and ethyl acetate volume ratio is developping agent column chromatography separated product, obtain the 2-Benzoylbenzene pinacol borate that structural formula is following, its productive rate is 94.5%.
3, linked reaction
0.69g (2.25mmol) 2-Benzoylbenzene pinacol borate is added successively in 20mL there-necked flask, 0.18g (0.5mmol) 1, 3, 5-(trisbromomethyl) benzene, 0.35g (2.5mmol) salt of wormwood, 1 of 10mL drying, 4-dioxane, 0.029g (0.025mmol) tetrakis triphenylphosphine palladium, under argon shield, 80 DEG C of stirring reactions 24 hours, be chilled to room temperature, neutrality is washed till with acetum, then with aqueous NaCl wash once, be extracted with ethyl acetate aqueous phase again three times, merge organic phase, with anhydrous sodium sulfate drying, rotary evaporation is except desolventizing, the mixed solution being 8:1 with sherwood oil and ethyl acetate volume ratio is developping agent column chromatography separated product, obtain structural formula following 1, 3, 5-tri-(((2-benzoyl) phenyl) methyl) benzene, productive rate 95.4%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (400MHz, CDCl
3+ TMS) δ (ppm): 7.62 (d, J=7.3Hz, 6H), 7.50 (t, J=7.4Hz, 3H), 7.36-7.27 (m, 9H), 7.22 (d, J=4.2Hz, 6H), 6.99 (d, J=7.6Hz, 3H), 6.48 (s, 3H), 3.76 (s, 6H);
13cNMR (100MHz, CDCl
3+ TMS) δ (ppm): 198.60,140.36,140.06,138.85,137.76,133.18,130.66,130.30,130.23,128.47,128.41,128.17,125.55,38.59; UHRMS-ESI (C
48h
36o
3) m/z: theoretical value 660.27, measured value ([M+Na]
+) 683.25.
4, reduction reaction
0.33g (0.5mmol) 1 is added successively in 50mL single port flask; 3; 5-tri-(((2-benzoyl) phenyl) methyl) benzene, 0.36mL (9mmol) methyl alcohol, 15mL methylene dichloride, 0.11g (3mmol) sodium borohydride; normal-temperature reaction; twice sodium borohydride (0.11g/ time) is added again in reaction process; coreaction is after 2 hours; with distilled water diluting 2 times; then three times are extracted with ethyl acetate; with anhydrous sodium sulfate drying; rotary evaporation is except desolventizing, and obtain the triol that structural formula is following, its productive rate is 100%.
5, ring closure reaction
The triol of 0.33g (0.5mmol) above-mentioned synthesis is dissolved in 90mL methylene dichloride, 0.02mL (0.45mmol) trifluoromethanesulfonic acid and 0.48mL (4.5mmol) trifluoroacetic anhydride is added under induction stirring, normal-temperature reaction 24 hours, then at 0 DEG C, the nitromethane solution that 5mL is dissolved with 0.19g (1.2mmol) FERRIC CHLORIDE ANHYDROUS is slowly dripped under argon shield, 0.68g (3.0mmol) DDQ is added again after dripping, stirring at normal temperature 30 minutes, add methyl alcohol cancellation reaction, by distilled water wash 3 ~ 5 removing FERRIC CHLORIDE ANHYDROUS, again by bisulfite saturated aqueous solution of sodium washing organic phase, organic phase anhydrous sodium sulfate drying, rotary evaporation is except desolventizing, compare for the mixed solution of 8:1 is for developping agent column chromatography separated product with sherwood oil and methylene chloride volume, obtain six vast Liu Ben Bing guans, productive rate is 92.2%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (400MHz, CDCl
3+ TMS) δ (ppm): 9.14-9.01 (m, 12H), 7.85-7.70 (m, 12H); MALDI-TOF-MS (C
48h
24) m/z: theoretical value 600.20, measured value (M
+) 600.40.
Embodiment 2
With following 2,10, the 18-trimethylammonium Liu Ben Bing guans of composite structure formula for example, concrete synthetic method is as follows:
1, friedel-crafts acylation
The methylene dichloride of 2.19g (10mmol) adjacent bromo-benzoyl chloride and 50mL drying is added in 100mL there-necked flask, at 0 DEG C, 1.33g (10mmol) aluminum trichloride (anhydrous) is added under argon shield, stirring reaction dissolves completely to aluminum chloride, 1.01g (11mmol) toluene is added again in mixed solution, 0 DEG C of stirring reaction 3 hours, solution is changed into orange-yellow by yellow, TLC tracking monitor is without raw material point, with saturated aqueous ammonium chloride cancellation reaction to neutral, with dichloromethane extraction three times, merge organic phase, anhydrous sodium sulfate drying, rotary evaporation is except desolventizing, the mixed solution being 10:1 with the volume ratio of sherwood oil and ethyl acetate is for developping agent column chromatography separated product, obtain the following clear oil compound of structural formula (2-bromophenyl) (4-aminomethyl phenyl) ketone, its productive rate is 91.2%.
2, boronation reaction
In the step 2 of embodiment 1; 2-bromine benzophenone used equimolar (2-bromophenyl) (4-aminomethyl phenyl) ketone is replaced; other steps are identical with embodiment 1; obtain white powdery solids compound 2-(4-methyl) the Benzoylbenzene pinacol borate that structural formula is following, its productive rate is 89.2%.
3, linked reaction
In the step 3 of embodiment 1; 2-Benzoylbenzene pinacol borate used equimolar 2-(4-methyl) Benzoylbenzene pinacol borate is replaced; other steps are identical with embodiment 1; obtain the yellow oily compound 1 that structural formula is following; 3; 5-tri-(((2-(4-methyl) benzoyl) phenyl) methyl) benzene, its productive rate is 88.4%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (600MHz, CDCl
3+ TMS) δ (ppm): 7.54 (d, J=7.9Hz, 6H), 7.30-7.26 (m, 3H), 7.21 (d, J=4.1Hz, 6H), 7.13 (d, J=7.9Hz, 6H), 6.96 (d, J=7.7Hz, 3H), 6.49 (s, 3H), 3.74 (s, 6H), 2.38 (s, 9H);
13cNMR (150MHz, CDCl
3+ TMS) δ (ppm): 198.22,144.00,140.21,139.75,139.03,135.11,130.39,130.29,129.94,129.03,128.11,128.08,125.37,77.24,77.03,76.82,38.44,21.71; UHRMS-ESI (C
51h
42o
3) m/z: theoretical value 702.31, measured value ([M+Na]
+) 725.30.
4, reduction reaction
In the step 4 of embodiment 1; used 1; 3; 5-tri-(((2-benzoyl) phenyl) methyl) benzene is with equimolar 1; 3,5-tri-(((2-(4-methyl) benzoyl) phenyl) methyl) benzene is replaced, and other steps are identical with embodiment 1; obtain the white powdery solids triol that structural formula is following, its productive rate is 98.6%.
5, ring closure reaction
In the step 5 of embodiment 1, the triol of Melbourne embodiment step 4 gained such as triol used is replaced, to add after DDQ normal-temperature reaction 120 minutes, other steps are identical with embodiment 1, obtain yellow powdery solid compound 2,10,18-trimethylammonium Liu Ben Bing guan, its productive rate is 69.2%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (300MHz, CDCl
3+ TMS) δ (ppm): 9.28-9.21 (m, 6H), 9.14 (d, J=8.4Hz, 3H), 9.05 (s, 3H), 7.86-7.78 (m, 6H), 7.63 (d, J=8.5Hz, 3H), 2.74 (s, 9H); MALDI-TOF-MS (C
51h
30) m/z: theoretical value 642.20, measured value (M
+) 642.30.
Embodiment 3
With following 2,10, the 18-trimethoxy Liu Ben Bing guans of composite structure formula for example, concrete synthetic method is as follows:
1, friedel-crafts acylation
In the step 1 of embodiment 2, the equimolar methyl-phenoxide of toluene used is replaced, 0 DEG C of stirring reaction 2 hours, other steps are identical with embodiment 2, obtain the following white powder compound of structural formula (2-bromophenyl) (4-p-methoxy-phenyl) ketone, its productive rate is 90.5%.
2, boronation reaction
In the step 2 of embodiment 1; 2-bromine benzophenone used equimolar (2-bromophenyl) (4-p-methoxy-phenyl) ketone is replaced; other steps are identical with embodiment 1; obtain white powdery solids compound 2-(4-methoxyl group) the Benzoylbenzene pinacol borate that structural formula is following, its productive rate is 90.7%.
3, linked reaction
In the step 3 of embodiment 1; 2-Benzoylbenzene pinacol borate used equimolar 2-(4-methoxyl group) Benzoylbenzene pinacol borate is replaced; other steps are identical with embodiment 1; obtain the yellow oily compound 1 that structural formula is following; 3; 5-tri-(((2-(4-methoxyl group) benzoyl) phenyl) methyl) benzene, its productive rate is 87.6%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (600MHz, CDCl
3+ TMS) δ (ppm): 7.60 (d, J=8.8Hz, 6H), 7.30-7.18 (m, 9H), 6.97 (d, J=7.4Hz, 3H), 6.80 (d, J=8.8Hz, 6H), 6.48 (s, 3H), 3.83 (s, 9H), 3.73 (s, 6H);
13cNMR (150MHz, CDCl
3+ TMS) δ (ppm): 197.23,163.63,140.18,139.48,139.26,132.48,130.53,130.37,129.74,128.02,127.83,125.40,113.57,55.49,38.44; UHRMS-ESI (C
51h
42o
6) m/z: theoretical value 750.30, measured value ([M+Na]
+) 773.29.
4, reduction reaction
In the step 4 of embodiment 1; used 1; 3; 5-tri-(((2-benzoyl) phenyl) methyl) benzene is with equimolar 1; 3,5-tri-(((2-(4-methoxyl group) benzoyl) phenyl) methyl) benzene is replaced, and other steps are identical with embodiment 1; obtain the white powdery solids triol that structural formula is following, its productive rate is 99.3%.
5, ring closure reaction
In the step 5 of embodiment 2, the triol of Melbourne embodiment step 4 gained such as triol used is replaced, and other steps are identical with embodiment 2, and obtain yellow powdery solid compound 2,10,18-trimethoxy Liu Ben Bing guan, its productive rate is 68.2%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (400MHz, CDCl
3+ TMS) δ (ppm): 9.31-9.28 (m, 3H), 9.15-9.10 (m, 6H), 8.67 (t, J=2.2Hz, 3H), 7.82-7.70 (m, 6H), 7.44-7.35 (m, 3H), 4.07 (s, 9H); MALDI-TOF-MS (C
51h
30o
3) m/z: theoretical value 690.20, measured value (M
+) 690.70.
Embodiment 4
With following 2,10, the 18-tri-tert Liu Ben Bing guans of composite structure formula for example, concrete synthetic method is as follows:
1, friedel-crafts acylation
In the step 1 of embodiment 3, the equimolar tert.-butylbenzene of methyl-phenoxide used is replaced, other steps are identical with embodiment 3, and obtain the following white powder compound of structural formula (2-bromophenyl) (4-tert-butyl-phenyl) ketone, its productive rate is 93.0%.
2, boronation reaction
In the step 2 of embodiment 1; 2-bromine benzophenone used equimolar (2-bromophenyl) (4-tert-butyl-phenyl) ketone is replaced; other steps are identical with embodiment 1; obtain white powdery solids compound 2-(the 4-tertiary butyl) the Benzoylbenzene pinacol borate that structural formula is following, its productive rate is 86.6%.
3, linked reaction
In the step 3 of embodiment 1; 2-Benzoylbenzene pinacol borate used equimolar 2-(the 4-tertiary butyl) Benzoylbenzene pinacol borate is replaced; other steps are identical with embodiment 1; obtain the yellow oily compound 1 that structural formula is following; 3; 5-tri-(((2-(the 4-tertiary butyl) benzoyl) phenyl) methyl) benzene, its productive rate is 92.3%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (300MHz, CDCl
3+ TMS) δ (ppm): 7.58 (d, J=8.4Hz, 6H), 7.37-7.27 (m, 9H), 7.22 (d, J=6.7Hz, 6H), 6.99 (d, J=7.5Hz, 3H), 6.51 (s, 3H), 3.75 (s, 6H), 1.30 (s, 27H);
13cNMR (75MHz, CDCl
3+ TMS) δ (ppm): 198.11,156.85,140.23,139.81,139.06,135.00,130.41,130.15,129.91,128.12,125.29,77.25,77.04,76.82,38.48,35.13,31.09; UHRMS-ESI (C
60h
60o
3) m/z: theoretical value 828.45, measured value ([M+Na]
+) 851.44.
4, reduction reaction
In the step 4 of embodiment 1; used 1; 3; 5-tri-(((2-benzoyl) phenyl) methyl) benzene is with equimolar 1; 3,5-tri-(((2-(the 4-tertiary butyl) benzoyl) phenyl) methyl) benzene is replaced, and other steps are identical with embodiment 1; obtain the white powdery solids compound triol that structural formula is following, its productive rate is 97.9%.
5, ring closure reaction
In the step 5 of embodiment 2, the triol of Melbourne embodiment step 4 gained such as triol used is replaced, and other steps are identical with embodiment 2, and obtain yellow powdery solid compound 2,10,18-tri-tert Liu Ben Bing guan, its productive rate is 74.2%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (600MHz, CDCl
3+ TMS) δ (ppm): 9.33-9.23 (m, 9H), 9.20 (dd, J=24.2,8.6Hz, 3H), 7.93-7.86 (m, 3H), 7.86-7.74 (m, 6H), 1.60 (s, 27H); MALDI-TOF-MS (C
60h
48) m/z: theoretical value 768.40, measured value (M
+) 768.40.
Embodiment 5
With following 2,10, the 18-triphenyl Liu Ben Bing guans of composite structure formula for example, concrete synthetic method is as follows:
1, friedel-crafts acylation
In the step 1 of embodiment 3, the equimolar biphenyl of methyl-phenoxide used is replaced, other steps are identical with embodiment 3, and obtain the following white powder compound of structural formula (2-bromophenyl) (4-phenyl) ketone, its productive rate is 90.3%.
2, boronation reaction
In the step 2 of embodiment 1; 2-bromine benzophenone used equimolar (2-bromophenyl) (4-phenyl) ketone is replaced; other steps are identical with embodiment 1; obtain white powdery solids compound 2-(4-phenyl) the Benzoylbenzene pinacol borate that structural formula is following, its productive rate is 85.3%.
3, linked reaction
In the step 3 of embodiment 1; 2-Benzoylbenzene pinacol borate used equimolar 2-(4-phenyl) Benzoylbenzene pinacol borate is replaced; other steps are identical with embodiment 1; obtain the pale yellow powder shape solid chemical compound 1 that structural formula is following; 3; 5-tri-(((2-(4-phenyl) benzoyl) phenyl) methyl) benzene, its yield is 91.0%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (600MHz, CDCl
3+ TMS) δ (ppm): 7.66 (d, J=8.3Hz, 6H), 7.57 (d, J=7.2Hz, 6H), 7.51 (d, J=8.3Hz, 6H), 7.45 (t, J=7.5Hz, 3H), 7.39 (t, J=7.3Hz, 3H), 7.29-7.23 (m, 9H), 7.20 (t, J=7.4Hz, 3H), 7.01 (d, J=7.7Hz, 3H), 6.52 (s, 3H), 3.78 (s, 6H);
13cNMR (150MHz, CDCl
3+ TMS) δ (ppm): 198.05,145.70,140.28,139.86,138.84,136.30,130.65,130.61,130.14,128.96,128.26,128.05,127.32,126.93,125.48,38.54; UHRMS-ESI (C
66h
48o
3) m/z: theoretical value 888.36, measured value ([M+Na]
+) 911.35.
4, reduction reaction
In the step 4 of embodiment 1; used 1; 3; 5-tri-(((2-benzoyl) phenyl) methyl) benzene is with equimolar 1; 3,5-tri-(((2-(4-phenyl) benzoyl) phenyl) methyl) benzene is replaced, and other steps are identical with embodiment 1; obtain the white powdery solids compound triol that structural formula is following, its productive rate is 98.6%.
5, ring closure reaction
In the step 5 of embodiment 2, the triol of Melbourne embodiment step 4 gained such as triol used is replaced, and other steps are identical with embodiment 2, and obtain yellow powdery solid compound 2,10,18-triphenyl Liu Ben Bing guan, its productive rate is 57.2%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (400MHz, CDCl
3+ TMS) δ (ppm): (t, J=7.7Hz, 3H), 9.25-9.10 (m, 9H), 8.01-7.90 (m, 3H), 7.82-7.70 (m, 12H), 7.51-7.46 (m, 6H), 7.41-7.36 (m, 3H); MALDI-TOF-MS (C
66h
36) m/z: theoretical value 828.30, measured value (M
+) 828.80.
Embodiment 6
With following 2,3,10,11,18, the 19-hexamethyl Liu Ben Bing guans of composite structure formula for example, concrete synthetic method is as follows:
1, friedel-crafts acylation
In the step 1 of embodiment 3, the equimolar o-Xylol of methyl-phenoxide used is replaced, and other steps are identical with embodiment 3, obtains the following white powder compound of structural formula (2-bromophenyl) (3,4-3,5-dimethylphenyl) ketone, its productive rate is 93.4%.
2, boronation reaction
In the step 2 of embodiment 1; equimolar (the 2-bromophenyl) (3 of 2-bromine benzophenone used; 4-3,5-dimethylphenyl) ketone replacement; other steps are identical with embodiment 1; obtain the white powdery solids compound 2-(3 that structural formula is following; 4-dimethyl) Benzoylbenzene pinacol borate, its productive rate is 91.4%.
3, linked reaction
In the step 3 of embodiment 1; the equimolar 2-(3 of 2-Benzoylbenzene pinacol borate used; 4-dimethyl) replacement of Benzoylbenzene pinacol borate; other steps are identical with embodiment 1; obtain structural formula following yellow oily compound 1,3,5-tri-(((2-(3; 4-dimethyl) benzoyl) phenyl) methyl) benzene, its productive rate is 82.4%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (600MHz, CDCl
3+ TMS) δ (ppm): 7.51 (s, 3H), 7.37 (d, J=7.8Hz, 3H), 7.30-7.28 (m, 3H), 7.26-7.21 (m, 6H), 7.10 (d, J=7.8Hz, 3H), 6.97 (d, J=7.5Hz, 3H), 6.54 (s, 3H), 3.77 (s, 6H), 2.31 (s, 9H), 2.24 (s, 9H);
13cNMR (150MHz, CDCl
3+ TMS) δ (ppm): 198.48,142.78,140.22,139.66,139.19,136.76,135.55,131.01,130.30,129.85,129.57,128.18,128.11,128.06,125.34,38.44,20.10,19.65; UHRMS-ESI (C
54h
48o
3) m/z: theoretical value 744.36, measured value ([M+Na]
+) 767.35.
4, reduction reaction
In the step 4 of embodiment 1; used 1; 3; 5-tri-(((2-benzoyl) phenyl) methyl) equimolar 1,3, the 5-tri-(((2-(3 of benzene; 4-dimethyl) benzoyl) phenyl) methyl) benzene replacement; other steps are identical with embodiment 1, and obtain the white powdery solids compound triol that structural formula is following, its productive rate is 98.5%.
5, ring closure reaction
In the step 5 of embodiment 2, the triol of Melbourne embodiment step 4 gained such as triol used is replaced, and other steps are identical with embodiment 2, and obtain yellow powdery solid compound 2,3,10,11,18,19-hexamethyl Liu Ben Bing guan, its productive rate is 74.2%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (300MHz, CDCl
3+ TMS) δ (ppm): 9.22 (s, 6H), 8.99 (s, 6H), 7.77 (s, 6H), 2.64 (s, 18H); MALDI-TOF-MS (C
54h
36) m/z: theoretical value 684.30, measured value (M
+) 684.40.
Embodiment 7
With the Isosorbide-5-Nitrae that composite structure formula is following, 9,12,17,20-hexa methoxy Liu Ben Bing guan is example, and concrete synthetic method is as follows:
1, friedel-crafts acylation
In the step 1 of embodiment 3, methyl-phenoxide used is replaced two methyl-phenoxides with equimolar, and other steps are identical with embodiment 3, obtain the following clear oil compound of structural formula (2-bromophenyl) (2,5-Dimethoxyphenyl) ketone, its productive rate is 90.8%.
2, boronation reaction
In the step 2 of embodiment 1; equimolar (the 2-bromophenyl) (2 of 2-bromine benzophenone used; 5-Dimethoxyphenyl) ketone replacement; other steps are identical with embodiment 1; obtain the white powdery solids compound 2-(2 that structural formula is following; 5-dimethoxy) Benzoylbenzene pinacol borate, its productive rate is 92.3%.
3, linked reaction
In the step 3 of embodiment 1; the equimolar 2-(2 of 2-Benzoylbenzene pinacol borate used; 5-dimethoxy) replacement of Benzoylbenzene pinacol borate; other steps are identical with embodiment 1; obtain structural formula following yellow oily compound 1,3,5-tri-(((2-(2; 5-dimethoxy) benzoyl) phenyl) methyl) benzene, its productive rate is 88.4%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (600MHz, CDCl
3+ TMS) δ (ppm): 7.18-7.16 (m, 6H), 7.05 (t, J=7.5Hz, 3H), 6.96 (d, J=7.7Hz, 3H), 6.91 (dd, J=8.9,3.1Hz, 3H), 6.87 (d, J=3.0Hz, 3H), 6.74 (d, J=8.9Hz, 3H), 6.70 (s, 3H), 4.04 (s, 6H), 3.66 (s, 9H), 3.39 (s, 9H);
13cNMR (150MHz, CDCl
3+ TMS) δ (ppm): 198.06,153.31,152.68,140.62,139.61,130.66,129.89,129.45,128.29,125.31,118.93,115.00,113.51,56.24,55.80,38.54; UHRMS-ESI (C
54h
48o
9) m/z: theoretical value 840.33, measured value ([M+Na]
+) 863.32.
4, reduction reaction
In the step 4 of embodiment 1; used 1; 3; 5-tri-(((2-benzoyl) phenyl) methyl) equimolar 1,3, the 5-tri-(((2-(2 of benzene; 5-dimethoxy) benzoyl) phenyl) methyl) benzene replacement; other steps are identical with embodiment 1, and obtain the white powdery solids compound triol that structural formula is following, its productive rate is 99.2%.
5, ring closure reaction
In the step 5 of embodiment 2, the triol of Melbourne embodiment step 4 gained such as triol used is replaced, and other steps are identical with embodiment 2, obtain yellow powdery solid compound Isosorbide-5-Nitrae, and 9,12,17,20-hexa methoxy Liu Ben Bing guan, its productive rate is 78.2%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (400MHz, CDCl
3+ TMS) δ (ppm): 3.83-3.89 (t, 18H), 7.34 (s, 6H), 7.40-7.44 (m, 6H), 8.25-8.28 (m, 6H); MALDI-TOF-MS (C
54h
36o
3) m/z: theoretical value 780.30, measured value (M
+) 780.10.
Embodiment 8
With the Isosorbide-5-Nitrae that composite structure formula is following, 9,12,17,20-hexamethyl Liu Ben Bing guan is example, and concrete synthetic method is as follows:
1, friedel-crafts acylation
In the step 1 of embodiment 1, the equimolar p-Xylol of benzene used is replaced, and other steps are identical with embodiment 1, obtains the following yellow powdery solid compound of structural formula (2-bromophenyl) (2,5-3,5-dimethylphenyl) ketone, its productive rate is 89.6%.
2, boronation reaction
In the step 2 of embodiment 1; equimolar (the 2-bromophenyl) (2 of 2-bromine benzophenone used; 5-3,5-dimethylphenyl) ketone replacement; other steps are identical with embodiment 1; obtain the yellow powdery solid compound 2-(2 that structural formula is following; 5-dimethyl) Benzoylbenzene pinacol borate, its productive rate is 90.2%.
3, linked reaction
In the step 3 of embodiment 1; the equimolar 2-(2 of 2-Benzoylbenzene pinacol borate used; 5-dimethyl) replacement of Benzoylbenzene pinacol borate; other steps are identical with embodiment 1; obtain structural formula following colorless oil compound 1,3,5-tri-(((2-(2; 5-dimethyl) benzoyl) phenyl) methyl) benzene, its productive rate is 83.4%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and Maxis high resolution mass spectrometer (Germany, Bruker company) characterize, and characterization data is as follows:
1hNMR (400MHz, CDCl
3+ TMS) δ (ppm): 7.26-7.22 (m, 6H), 7.19-7.13 (m, 6H), 7.10 (d, J=7.8Hz, 3H), 7.02 (d, J=7.1Hz, 3H), 6.94 (s, 3H), 6.67 (s, 3H), 4.01 (s, 6H), 2.26 (s, 9H), 2.19 (s, 9H);
13cNMR (100MHz, CDCl
3+ TMS) δ (ppm): 200.78,140.87,140.56,139.33,138.64,135.28,134.86,131.92,131.27,131.06,130.87,130.06,128.28,125.65,38.66,20.77,20.21; UHRMS-ESI (C
54h
48o
3) m/z: theoretical value 744.36, measured value ([M+Na]
+) 767.35.
4, reduction reaction
In the step 4 of embodiment 1; used 1; 3; 5-tri-(((2-benzoyl) phenyl) methyl) equimolar 1,3, the 5-tri-(((2-(2 of benzene; 5-dimethyl) benzoyl) phenyl) methyl) benzene replacement; other steps are identical with embodiment 1, and obtain the white powdery solids compound triol that structural formula is following, its productive rate is 97.3%.
5, ring closure reaction
In the step 5 of embodiment 2, the triol of Melbourne embodiment step 4 gained such as triol used is replaced, and other steps are identical with embodiment 2, obtain yellow powdery solid compound Isosorbide-5-Nitrae, and 9,12,17,20-hexamethyl Liu Ben Bing guan, its productive rate is 55.6%.
Products therefrom Avance type superconduction fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and MALDI-TOF mass spectrograph (Germany, BurkerDaltonics) characterize, and characterization data is as follows:
1hNMR (400MHz, CDCl
3+ TMS) δ (ppm): 2.65-2.85 (m, 18H), 7.53-7.72 (m, 10H), 8.21-8.29 (m, 4H), 8.99-9.22 (m, 4H); MALDI-TOF-MS (C
54h
36) m/z: theoretical value 684.30, measured value (M
+) 684.50.
Claims (8)
1. synthesize six vast position six benzene and a method for guan and derivative thereof, it is characterized in that it is made up of following step:
(1) friedel-crafts acylation
Adjacent bromo-benzoyl chloride is dissolved in methylene dichloride completely, 0 DEG C, add aluminum chloride and formula 1 compound under argon shield, the mol ratio of adjacent bromo-benzoyl chloride and aluminum chloride, formula 1 compound is 1:1 ~ 1.5:1 ~ 1.5,0 DEG C or stirring at normal temperature reaction 2 ~ 3 hours, react with saturated ammonium chloride cancellation, separation and purification product, obtains formula 2 compound;
(2) boronation reaction
With 1,4-dioxane is solvent, under argon shield, by formula 2 compound, connection pinacol borate, Potassium ethanoate, [1, two (diphenylphosphino) ferrocene of 1'-] palladium chloride is 1:1.0 ~ 2.0:1.5 ~ 2.5:0.03 ~ 0.1 in molar ratio, 80 ~ 100 DEG C of stirring reactions 12 ~ 24 hours, separation and purification product, obtains formula 3 compound;
(3) linked reaction
With 1,4-dioxane is solvent, under argon shield, by 1,3,5-(trisbromomethyl) benzene, formula 3 compound, salt of wormwood, tetrakis triphenylphosphine palladium are 1:3 ~ 5:4 ~ 6:0.03 ~ 0.1 in molar ratio, 80 ~ 100 DEG C of stirring reactions 12 ~ 24 hours, separation and purification product, obtains formula 4 compound;
(4) reduction reaction
Taking methylene dichloride as solvent, is 1:12 ~ 20:12 ~ 20 by formula 4 compound, methyl alcohol, sodium borohydride in molar ratio, normal-temperature reaction 1 ~ 2 hour, and separation and purification product, obtains formula 5 compound;
(5) ring closure reaction
Formula 5 compound is dissolved in methylene dichloride completely, add trifluoroacetic anhydride and trifluoromethanesulfonic acid, stirring at normal temperature 24 ~ 48 hours, then at 0 DEG C, the nitromethane solution of FERRIC CHLORIDE ANHYDROUS is dripped under argon shield, DDQ is added after dripping, formula 5 compound and trifluoroacetic anhydride, trifluoromethanesulfonic acid, FERRIC CHLORIDE ANHYDROUS, the mol ratio of DDQ is 1:7 ~ 10:0.5 ~ 1.0:2 ~ 3:5 ~ 7, 0 DEG C or stirring at normal temperature 30 ~ 120 minutes, add methyl alcohol cancellation reaction, separation and purification product, prepare six vast position six benzene shown in an accepted way of doing sth 6 and guan or derivatives thereof,
In above-mentioned formula 1 ~ formula 6 compound, R
1, R
2, R
3, R
4independently represent separately in H, alkyl, alkoxyl group, phenyl, alkyl-substituted phenyl, alkoxy substituted phenyl any one.
2. the method for synthesis according to claim 1 six vast Liu Ben Bing guans and derivative thereof, is characterized in that: in described formula 1 ~ formula 6 compound, R
1, R
2, R
3, R
4independently represent H, C separately
1~ C
4alkyl, C
1~ C
4any one in alkoxyl group, phenyl.
3. the method for synthesis according to claim 1 six vast Liu Ben Bing guans and derivative thereof, is characterized in that: in described formula 1 ~ formula 6 compound, R
1, R
2, R
3, R
4independently represent separately in H, methyl, methoxyl group, phenyl any one.
4. the method for six vast the Liu Ben Bing guans of the synthesis according to claims 1 to 3 any one and derivative thereof, is characterized in that: in described step (1), and the mol ratio of adjacent bromo-benzoyl chloride and aluminum chloride, formula 1 compound is 1:1:1.1.
5. the method for six vast the Liu Ben Bing guans of the synthesis according to claims 1 to 3 any one and derivative thereof, it is characterized in that: in described step (2), formula 2 compound is 1:1.5:2:0.05 with the mol ratio of connection pinacol borate, Potassium ethanoate, [two (diphenylphosphino) ferrocene of 1,1'-] palladium chloride.
6. the method for six vast the Liu Ben Bing guans of the synthesis according to claims 1 to 3 any one and derivative thereof, it is characterized in that: in described step (3), 1, the mol ratio of 3,5-(trisbromomethyl) benzene and formula 3 compound, salt of wormwood, tetrakis triphenylphosphine palladium is 1:4.5:5:0.05.
7. the method for six vast the Liu Ben Bing guans of the synthesis according to claims 1 to 3 any one and derivative thereof, is characterized in that: in described step (4), and the mol ratio of formula 4 compound and methyl alcohol, sodium borohydride is 1:18:18.
8. the method for six vast the Liu Ben Bing guans of the synthesis according to claims 1 to 3 any one and derivative thereof, it is characterized in that: in described step (5), the mol ratio of formula 5 compound and trifluoroacetic anhydride, trifluoromethanesulfonic acid, FERRIC CHLORIDE ANHYDROUS, DDQ is 1:9:0.9:2.4:6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129276A (en) * | 2017-12-21 | 2018-06-08 | 上海师范大学 | A kind of preparation method of sandy beach chair form and nine benzene compounds |
| KR20200111048A (en) * | 2019-03-18 | 2020-09-28 | 울산과학기술원 | An Anodic Active Material Comprising Contorted Hexabenzocoronene Derivative, Method Of Manufacturing Anode Using Thereof, And Secondary Battery Comprising The Same |
| US20210179519A1 (en) * | 2019-12-16 | 2021-06-17 | Samsung Sdi Co., Ltd. | Compound, synthesis method of the compound, hardmask composition, and method of forming patterns |
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| CN101967147A (en) * | 2010-09-15 | 2011-02-09 | 陕西师范大学 | S-triazacoronene compound and synthesis method and application thereof |
| CN103265436A (en) * | 2013-05-27 | 2013-08-28 | 陕西师范大学 | Method for synthesising 1,5,9-trinitro-2,3,6,7,10,11-hexa-alkoxy triphenylene |
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| CN101967147A (en) * | 2010-09-15 | 2011-02-09 | 陕西师范大学 | S-triazacoronene compound and synthesis method and application thereof |
| CN103265436A (en) * | 2013-05-27 | 2013-08-28 | 陕西师范大学 | Method for synthesising 1,5,9-trinitro-2,3,6,7,10,11-hexa-alkoxy triphenylene |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129276A (en) * | 2017-12-21 | 2018-06-08 | 上海师范大学 | A kind of preparation method of sandy beach chair form and nine benzene compounds |
| CN108129276B (en) * | 2017-12-21 | 2020-10-13 | 上海师范大学 | Preparation method of beach chair type nonabenzene compound |
| KR20200111048A (en) * | 2019-03-18 | 2020-09-28 | 울산과학기술원 | An Anodic Active Material Comprising Contorted Hexabenzocoronene Derivative, Method Of Manufacturing Anode Using Thereof, And Secondary Battery Comprising The Same |
| KR102165013B1 (en) * | 2019-03-18 | 2020-10-13 | 울산과학기술원 | An Anodic Active Material Comprising Contorted Hexabenzocoronene Derivative, Method Of Manufacturing Anode Using Thereof, And Secondary Battery Comprising The Same |
| US20210179519A1 (en) * | 2019-12-16 | 2021-06-17 | Samsung Sdi Co., Ltd. | Compound, synthesis method of the compound, hardmask composition, and method of forming patterns |
| CN112979408A (en) * | 2019-12-16 | 2021-06-18 | 三星Sdi株式会社 | Compound and synthesis method thereof, hard mask composition and method for forming pattern |
| JP2021095392A (en) * | 2019-12-16 | 2021-06-24 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Compound, synthesis method of compound, hardmask composition, and method of forming patterns |
| JP7097424B2 (en) | 2019-12-16 | 2022-07-07 | 三星エスディアイ株式会社 | Compounds, compound synthesis methods, hardmask compositions and pattern forming methods |
| CN112979408B (en) * | 2019-12-16 | 2024-02-09 | 三星Sdi株式会社 | Compound and its synthesis method, hard mask composition and pattern forming method |
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