CN105061135B - A kind of synthesis six vast position six benzos and the method for derivative thereof - Google Patents
A kind of synthesis six vast position six benzos and the method for derivative thereof Download PDFInfo
- Publication number
- CN105061135B CN105061135B CN201510450696.2A CN201510450696A CN105061135B CN 105061135 B CN105061135 B CN 105061135B CN 201510450696 A CN201510450696 A CN 201510450696A CN 105061135 B CN105061135 B CN 105061135B
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- derivative
- reaction
- benzos
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the method for a kind of synthesis six vast position six benzos and derivative thereof, the method is with bromophenyl formyl chloride as raw material, carry out friedel-crafts acylation with benzene or substituent benzene, boronation reaction obtains 2 Benzoylbenzene pinacol borates and derivative thereof, further with 1, 3, 5 (trisbromomethyl) benzene is constructed the skeleton 1 of c HBC by Suzuki coupling reaction, 3, 5 three (((2 benzoyl) phenyl) methyl) benzene and its derivative, pass sequentially through reduction reaction again, Friedel-Crafts reaction, Scholl cyclization synthesis six vast position six benzos and derivative thereof.Reaction condition 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 synthesized vast position six benzo derivatives are the method for synthesis six vast position six benzo of a kind of simplicity and derivative thereof without alkoxyl as guiding base and positioning base.
Description
Technical field
The invention belongs to the synthesis technical field of polycyclic aromatic hydrocarbon compounds, be specifically related to a kind of six vast position six benzos
(hexa-cata-hexabenzocoronene, c-HBC) compound and the synthetic method of derivative thereof.
Background technology
The aromatic core of c-HBC and derivative thereof is distortion, and the distortion carbon atom of its planar central carbon atom near-end is because of sky
Between crowded and deviate 20 ° of plane, structurally in concave-concave conformation, compound that can be special with some, such as C60,
Form the complementary complex compound of geometry.C-HBC also has the construction 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 a kind of
Potential column liquid crystal core, has good electron-transporting and good luminescence generated by light effect, and scene effect is brilliant
Body pipe, organic semiconducting materials, photovoltaic cell and photodiode have potential extensive application.
The synthesis of c-HBC in nineteen sixty-five reported first of Clar seminar (Tetrahedron 1965,21,
467-470).They are first prepared for the framework as target molecule for a kind of tetraalkoxide compound, then by this compound with
Copper powder mixes, and reacts and i.e. can get c-HBC, obtain product through column chromatography for separation, yield only about 2% at 400 DEG C.
The c-HBC of report and the best acquisition methods of derivative thereof have two kinds at present, and one is Nuckolls seminar
Development with pentacene quinone as raw material, through double Barton-Kelloggolefination reaction, or with virtue boric acid
Carry out the Suzuki coupling reaction of quadruple, obtain c-HBC and symmetrical the spreading out of minute surface thereof by Sholl cyclization further
Biological (Angew.Chem.Int.Ed.2005,44,7390-7394；Org.Lett., 2009,11:2225-2228；
Chem.Sci., 2011,2,1480-1486).But raw materials used being difficult to of the method obtains, and expensive, difficult
Produce with a large amount of, the synthesis of the c-HBC derivative of different symmetry requirement cannot be met simultaneously.Another kind of method
It is the synthetic method (J.Am.Chem. that 2014 Nian Weijunfa seminar report a kind of c-HBC and derivative thereof
Soc., 2014,136:5057-5064).The method is with 1, and 3,5-(trisbromomethyl) benzene is raw material, with electron rich virtue
1,3,5-tri-(the 3,4-dialkoxy benzyl that boric acid obtains the base containing positioning through triple Suzuki coupling reactions and guides base
Base) center framework of benzene, and then occur Fu Ke-aromatisation-dehydrocyclization to react with aromatic aldehyde, obtain three-fold symmetry
C-HBC derivative.The intermediate of the method needs activated group alkoxyl as guiding base, for simple c-HBC
Then cannot realize as the synthesis of the c-HBC derivative guiding base with without activation base.
Content of the invention
Technical problem solved by the invention is to overcome above-mentioned six vast position six benzos and derivative synthesizing process thereof
Shortcoming, provide a kind of cheaper starting materials to be easy to get, synthesis step is simple and direct, low in the pollution of the environment, mild condition, can be a large amount of
Produce and yield height, the synthetic method being not necessarily to six vast position six benzos as guiding base for the alkoxyl and derivative thereof.
The synthetic route solving the technical scheme that above-mentioned technical problem uses is as follows:
In above-mentioned formula 1～formula 6 compound, R1、R2、R3、R4Each independent representative H, alkyl, alkoxyl,
Any one in phenyl, alkyl-substituted phenyl, alkoxy substituted phenyl, preferably R1、R2、R3、R4Each
Independent representative H, C1～C4Alkyl, C1～C4Any one in alkoxyl, phenyl, further preferred R1、
R2、R3、R4Any one in each independent representative H, methyl, methoxyl group, phenyl.
Concrete synthetic method is made up of following step:
1st, friedel-crafts acylation
Be dissolved completely in bromophenyl formyl chloride in dichloromethane, 0 DEG C, add under argon shield alchlor and
Formula 1 compound, bromophenyl formyl chloride is 1:1～1.5:1～1.5 with alchlor, the mol ratio of formula 1 compound,
0 DEG C or stirring at normal temperature are reacted 2～3 hours, with saturated ammonium chloride cancellation reaction, isolated and purified product, obtain formula 2
Compound.
2nd, boronation reaction
With Isosorbide-5-Nitrae-dioxane as solvent, under argon shield, by formula 2 compound, connection pinacol borate, vinegar
Acid potassium, [1,1'-double (diphenylphosphino) ferrocene] palladium chloride in molar ratio for 1:1.0～2.0:1.5～2.5:0.03～
0.1,80～100 DEG C are stirred reaction 12～24 hours, isolated and purified product, obtain formula 3 compound.
3rd, coupling reaction
With Isosorbide-5-Nitrae-dioxane as solvent, under argon shield, by 1,3,5-(trisbromomethyl) benzene, formula 3 compound,
Potassium carbonate, 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, isolated and purified product, obtain formula 4 compound.
4th, reduction reaction
With dichloromethane as solvent, by formula 4 compound, methyl alcohol, sodium borohydride in molar ratio for 1:12～20:12～
20, normal-temperature reaction 1～2 hour, isolated and purified product, obtain formula 5 compound.
5th, ring closure reaction
Being dissolved completely in formula 5 compound in dichloromethane, adding TFAA and TFMS, normal temperature stirs
Mix 24～48 hours, then 0 DEG C, the nitromethane solution of dropping anhydrous ferric trichloride, dropping under argon shield
Add DDQ after complete, formula 5 compound and TFAA, TFMS, anhydrous ferric trichloride,
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
Minute, add methyl alcohol cancellation reaction, isolated and purified product, preparation six vast position six benzos shown in an accepted way of doing sth 6 or its
Derivative.
In above-mentioned steps 1, preferably bromophenyl formyl chloride and alchlor, the mol ratio of formula 1 compound are 1:1:1.1.
In above-mentioned steps 2, preferred formula 2 compound and connection pinacol borate, potassium acetate, [1,1'-double (diphenylphosphines
Base) ferrocene] mol ratio of palladium chloride is 1:1.5:2:0.05.
In above-mentioned steps 3, preferably 1,3,5-(trisbromomethyl) benzene and formula 3 compound, potassium carbonate, four (triphenylphosphines)
The mol ratio of palladium is 1:4.5:5:0.05.
In above-mentioned steps 4, preferred formula 4 compound is 1:18:18 with methyl alcohol, the mol ratio of sodium borohydride.
In above-mentioned steps 5, preferred formula 5 compound and TFAA, TFMS, anhydrous ferric trichloride,
The mol ratio of DDQ is 1:9:0.9:2.4:6.
Reaction condition of the present invention is gentle, and easy to operate, product total recovery reaches as high as more than 80%, can produce in a large number,
Six synthesized vast position six benzo derivatives are the conjunction of a kind of simplicity without alkoxyl as guiding base and positioning base
Become the method for six vast position six benzos and derivative thereof.
Detailed description of the invention
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
Embodiment.
Embodiment 1
As a example by six following vast position six benzos of composite structure formula, concrete synthetic method is as follows:
1st, friedel-crafts acylation
The dichloro that 2.19g (10mmol) bromophenyl formyl chloride and 50mL are dried is added in 100mL there-necked flask
Methane, 0 DEG C, under argon shield, add 1.33g (10mmol) alchlor and 8.59g (11mmol) benzene,
Stirring at normal temperature is reacted 3 hours, with saturated ammonium chloride cancellation reaction, extracts three times with dichloromethane, merges organic phase,
Being dried with anhydrous sodium sulfate, rotary evaporation removes solvent, with the volume ratio of petroleum ether and ethyl acetate as 10:1
Mixed liquor is solvent column chromatography separation product, obtains the following 2-bromine benzophenone of structural formula, and its productivity is
98.2%.
2nd, boronation reaction
Be sequentially added into 1.30g (5mmol) 2-bromine benzophenone in 50mL there-necked flask, 1.90g (7.5mmol) joins boron
Acid pinacol ester, 0.98g (10mmol) potassium acetate, 0.18g (0.25mmol) [double (diphenylphosphino) ferrocene of 1,1'-]
Isosorbide-5-Nitrae-dioxane that palladium chloride, 25mL are dried, under argon shield, 100 DEG C of stirrings are reacted 24 hours,
It is cooled to room temperature, adds distilled water diluting 2 times, be extracted with ethyl acetate three times, merge organic phase, use anhydrous slufuric acid
Sodium is dried, and rotary evaporation removes solvent, with petroleum ether and the mixed liquor as 20:1 for the ethyl acetate volume ratio for launching
Agent column chromatography separation product, obtains the following 2-Benzoylbenzene pinacol borate of structural formula, and its productivity is
94.5%.
3rd, coupling reaction
Be sequentially added in 20mL there-necked flask 0.69g (2.25mmol) 2-Benzoylbenzene pinacol borate,
The 1,4-dioxy that 0.18g (0.5mmol) 1,3,5-(trisbromomethyl) benzene, 0.35g (2.5mmol) potassium carbonate, 10mL are dried
Six rings, 0.029g (0.025mmol) tetrakis triphenylphosphine palladium, under argon shield, 80 DEG C of stirrings are reacted 24 hours,
It is cooled to room temperature, is washed till neutrality with acetum, then washed once with sodium-chloride water solution, then extract with ethyl acetate
Water intaking phase three times, merges organic phase, is dried with anhydrous sodium sulfate, and rotary evaporation removes solvent, with petroleum ether and second
Acetoacetic ester volume ratio be the mixed liquor of 8:1 be solvent column chromatography separation product, obtain structural formula following
1,3,5-tri-(((2-benzoyl) phenyl) methyl) benzene, productivity 95.4%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:
1H NMR (400MHz, CDCl3+ 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)；13C NMR (100MHz, CDCl3+ 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(C48H36O3) m/z: theoretical value 660.27, measured value ([M+Na]+)683.25。
4th, reduction reaction
It is sequentially added into 0.33g (0.5mmol) 1,3,5-tri-(((2-benzoyl) phenyl) methyl) in 50mL single port flask
Benzene, 0.36mL (9mmol) methyl alcohol, 15mL dichloromethane, 0.11g (3mmol) sodium borohydride, normal-temperature reaction,
Adding sodium borohydride (0.11g/ time) twice in course of reaction again, coreaction is after 2 hours, with distilled water diluting 2 times,
Then being extracted with ethyl acetate three times, being dried with anhydrous sodium sulfate, rotary evaporation removes solvent, obtains structural formula such as
Under triol, its productivity is 100%.
5th, ring closure reaction
It is dissolved in the triol of above-mentioned for 0.33g (0.5mmol) synthesis in 90mL dichloromethane, add under electromagnetic agitation
0.02mL (0.45mmol) TFMS and 0.48mL (4.5mmol) TFAA, normal-temperature reaction 24 hours,
Then 0 DEG C, be slowly added dropwise the nitre that 5mL is dissolved with 0.19g (1.2mmol) anhydrous ferric trichloride under argon shield
Methylmethane solution, adds 0.68g (3.0mmol) DDQ after dripping, stirring at normal temperature 30 minutes,
Add methyl alcohol cancellation reaction, wash 3～5 times with distilled water and remove anhydrous ferric trichloride, then satisfied by sodium hydrogensulfite
With solution washing organic phase, organic phase anhydrous sodium sulfate is dried, rotary evaporation remove solvent, with petroleum ether with
Methylene chloride volume is solvent column chromatography separation product than the mixed liquor for 8:1, obtains six vast position six benzos
, productivity is 92.2%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1H NMR (400MHz, CDCl3+ TMS) δ (ppm): 9.14-9.01 (m, 12H), 7.85-7.70 (m,
12H)；MALDI-TOF-MS(C48H24) m/z: theoretical value 600.20, measured value (M+)600.40。
Embodiment 2
As a example by following 2,10,18-trimethyl six benzos of composite structure formula, concrete synthetic method is as follows:
1st, friedel-crafts acylation
The dichloromethane that 2.19g (10mmol) bromophenyl formyl chloride and 50mL are dried is added in 100mL there-necked flask
Alkane, 0 DEG C, add 1.33g (10mmol) aluminum trichloride (anhydrous) under argon shield, stirring reaction is complete to alchlor
CL, then in mixed liquor, add 1.01g (11mmol) toluene, 0 DEG C of stirring is reacted 3 hours, and solution is by yellow
Being changed into orange-yellow, TLC tracking and monitoring, without raw material point, with saturated aqueous ammonium chloride cancellation reaction to neutral, is used
Dichloromethane extracts three times, merges organic phase, and anhydrous sodium sulfate is dried, and rotary evaporation removes solvent, with petroleum ether
It is that solvent column chromatography separates product with the mixed liquor that the volume ratio of ethyl acetate is 10:1, obtain structural formula
Following clear oil compound (2-bromophenyl) (4-aminomethyl phenyl) ketone, its productivity is 91.2%.
2nd, boronation reaction
In the step 2 of embodiment 1,2-bromine benzophenone used equimolar (2-bromophenyl) (4-methylbenzene
Base) ketone replacement, other steps are same as in Example 1, obtain the following white powdery solids compound of structural formula
2-(4-methyl) Benzoylbenzene pinacol borate, its productivity is 89.2%.
3rd, coupling reaction
In the step 3 of embodiment 1,2-Benzoylbenzene pinacol borate used is with equimolar 2-(4-
Methyl) replacement of Benzoylbenzene pinacol borate, other steps are same as in Example 1, obtain structural formula following
Yellow oily compound 1,3,5-tri-(((2-(4-methyl) benzoyl) phenyl) methyl) benzene, its productivity is 88.4%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:
1H NMR (600MHz, CDCl3+ 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)；13C NMR (150MHz, CDCl3+ 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(C51H42O3) m/z:
Theoretical value 702.31, measured value ([M+Na]+)725.30。
4th, reduction reaction
In the step 4 of embodiment 1, used 1,3,5-tri-(((2-benzoyl) phenyl) methyl) benzene equimolar
1,3,5-tri-(((2-(4-methyl) benzoyl) phenyl) methyl) benzene replace, other steps are same as in Example 1,
To the following white powdery solids triol of structural formula, its productivity is 98.6%.
5th, ring closure reaction
In the step 5 of embodiment 1, the triol used triol of equimolar the present embodiment step 4 gained is replaced,
Normal-temperature reaction 120 minutes after addition DDQ, other steps are same as in Example 1, obtain yellow powder
Powder solid chemical compound 2,10,18-trimethyl six benzo, its productivity is 69.2%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1HNMR (300MHz, CDCl3+ 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(C51H30) m/z: theoretical value 642.20, measured value (M+)642.30。
Embodiment 3
As a example by following 2,10,18-trimethoxy six benzos of composite structure formula, concrete synthetic method is as follows:
1st, friedel-crafts acylation
In the step 1 of embodiment 2, toluene used is replaced by equimolar methyl phenyl ethers anisole, 0 DEG C of stirring reaction 2
Hour, other steps are same as in Example 2, obtain structural formula following white powder compound (2-bromophenyl) (4-
Methoxyphenyl) ketone, its productivity is 90.5%.
2nd, boronation reaction
In the step 2 of embodiment 1,2-bromine benzophenone used equimolar (2-bromophenyl) (4-methoxyl group
Phenyl) ketone replacement, other steps are same as in Example 1, obtain the following white powdery solids chemical combination of structural formula
Thing 2-(4-methoxyl group) Benzoylbenzene pinacol borate, its productivity is 90.7%.
3rd, coupling reaction
In the step 3 of embodiment 1,2-Benzoylbenzene pinacol borate used is with equimolar 2-(4-
Methoxyl group) replacement of Benzoylbenzene pinacol borate, other steps are same as in Example 1, obtain structural formula as follows
Yellow oily compound 1,3,5-tri-(((2-(4-methoxyl group) benzoyl) phenyl) methyl) benzene, its productivity is 87.6%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:
1H NMR (600MHz, CDCl3+ 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)；13C NMR (150MHz, CDCl3+ 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(C51H42O6) m/z: theoretical value 750.30, measured value ([M+Na]+)773.29。
4th, 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 same as in Example 1, obtain
The following white powdery solids triol of structural formula, its productivity is 99.3%.
5th, ring closure reaction
In the step 5 of embodiment 2, the triol used triol of equimolar the present embodiment step 4 gained is replaced,
Other steps are same as in Example 2, obtain yellow powdery solid compound 2,10,18-trimethoxy six benzo,
Its productivity is 68.2%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1H NMR (400MHz, CDCl3+ 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(C51H30O3) m/z: theoretical value 690.20, measured value (M+)690.70。
Embodiment 4
As a example by following 2,10,18-tri-tert six benzos of composite structure formula, concrete synthetic method is as follows:
1st, friedel-crafts acylation
In the step 1 of embodiment 3, methyl phenyl ethers anisole used is replaced by equimolar tert-butyl benzene, other steps with
Embodiment 3 is identical, obtains structural formula following white powder compound (2-bromophenyl) (4-tert-butyl-phenyl) ketone,
Its productivity is 93.0%.
2nd, boronation reaction
In the step 2 of embodiment 1,2-bromine benzophenone used equimolar (2-bromophenyl) (the 4-tert-butyl group
Phenyl) ketone replacement, other steps are same as in Example 1, obtain the following white powdery solids chemical combination of structural formula
Thing 2-(the 4-tert-butyl group) Benzoylbenzene pinacol borate, its productivity is 86.6%.
3rd, coupling reaction
In the step 3 of embodiment 1,2-Benzoylbenzene pinacol borate used is with equimolar 2-(4-
The tert-butyl group) replacement of Benzoylbenzene pinacol borate, other steps are same as in Example 1, obtain structural formula as follows
Yellow oily compound 1,3,5-tri-(((2-(the 4-tert-butyl group) benzoyl) phenyl) methyl) benzene, its productivity is 92.3%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:
1H NMR (300MHz, CDCl3+ 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)；13C NMR (75MHz, CDCl3+ 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(C60H60O3) m/z: theoretical value 828.45, measured value ([M+Na]+)851.44。
4th, 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-tert-butyl group) benzoyl) phenyl) methyl) benzene is replaced, and other steps are same as in Example 1,
To the following white powdery solids compound triol of structural formula, its productivity is 97.9%.
5th, ring closure reaction
In the step 5 of embodiment 2, the triol used triol of equimolar the present embodiment step 4 gained is replaced,
Other steps are same as in Example 2, obtain yellow powdery solid compound 2,10,18-tri-tert six benzo,
Its productivity is 74.2%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1H NMR (600MHz, CDCl3+ 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(C60H48) m/z: theoretical value 768.40, measured value (M+)768.40。
Embodiment 5
As a example by following 2,10,18-triphenyl six benzos of composite structure formula, concrete synthetic method is as follows:
1st, friedel-crafts acylation
In the step 1 of embodiment 3, methyl phenyl ethers anisole used is replaced by equimolar biphenyl, other steps and enforcement
Example 3 is identical, obtains structural formula following white powder compound (2-bromophenyl) (4-phenyl) ketone, and it produces
Rate is 90.3%.
2nd, boronation reaction
In the step 2 of embodiment 1,2-bromine benzophenone used equimolar (2-bromophenyl) (4-phenyl benzene
Base) ketone replacement, other steps are same as in Example 1, obtain the following white powdery solids compound of structural formula
2-(4-phenyl) Benzoylbenzene pinacol borate, its productivity is 85.3%.
3rd, coupling reaction
In the step 3 of embodiment 1,2-Benzoylbenzene pinacol borate used is with equimolar 2-(4-
Phenyl) replacement of Benzoylbenzene pinacol borate, other steps are same as in Example 1, obtain structural formula following
Pale yellow powder shape solid chemical compound 1,3,5-tri-(((2-(4-phenyl) benzoyl) phenyl) methyl) benzene, its yield is
91.0%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:1H NMR(600
MHz, CDCl3+ 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)；13C NMR(150
MHz, CDCl3+ 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(C66H48O3) m/z: theoretical value 888.36, measured value ([M+Na]+)911.35。
4th, 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 same as in Example 1, obtain
The following white powdery solids compound triol of structural formula, its productivity is 98.6%.
5th, ring closure reaction
In the step 5 of embodiment 2, the triol used triol of equimolar the present embodiment step 4 gained is replaced,
Other steps are same as in Example 2, obtain yellow powdery solid compound 2,10,18-triphenyl six benzo,
Its productivity is 57.2%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1H NMR (400MHz, CDCl3+ 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(C66H36) m/z: theoretical value 828.30, measured value (M+)828.80。
Embodiment 6
As a example by following 2,3,10,11,18,19-hexamethyl six benzos of composite structure formula, concrete synthetic method is as follows:
1st, friedel-crafts acylation
In the step 1 of embodiment 3, methyl phenyl ethers anisole used is replaced by equimolar ortho-xylene, other steps with
Embodiment 3 is identical, obtains structural formula following white powder compound (2-bromophenyl) (3,4-3,5-dimethylphenyl) first
Ketone, its productivity is 93.4%.
2nd, boronation reaction
In the step 2 of embodiment 1,2-bromine benzophenone used equimolar (2-bromophenyl) (3,4-diformazans
Base phenyl) ketone replacement, other steps are same as in Example 1, obtain the following white powdery solids of structural formula
Compound 2-(3,4-dimethyl) Benzoylbenzene pinacol borate, its productivity is 91.4%.
3rd, coupling reaction
In the step 3 of embodiment 1,2-Benzoylbenzene pinacol borate used is with equimolar 2-(3,4-
Dimethyl) replacement of Benzoylbenzene pinacol borate, other steps are same as in Example 1, obtain structural formula as follows
Yellow oily compound 1,3,5-tri-(((2-(3,4-dimethyl) benzoyl) phenyl) methyl) benzene, its productivity is
82.4%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:
1H NMR (600MHz, CDCl3+ 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)；13C NMR (150MHz,
CDCl3+ 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(C54H48O3) m/z: theoretical value 744.36, measured value ([M+Na]+)767.35。
4th, 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-(3,4-dimethyl) benzoyl) phenyl) methyl) benzene is replaced, and other steps are same as in Example 1,
To the following white powdery solids compound triol of structural formula, its productivity is 98.5%.
5th, ring closure reaction
In the step 5 of embodiment 2, the triol used triol of equimolar the present embodiment step 4 gained is replaced,
Other steps are same as in Example 2, obtain yellow powdery solid compound 2,3,10,11,18,19-hexamethyl six benzene
And, its productivity is 74.2%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1H NMR (300MHz, CDCl3+ TMS) δ (ppm): 9.22 (s, 6H), 8.99 (s, 6H), 7.77 (s,
6H), 2.64 (s, 18H)；MALDI-TOF-MS(C54H36) m/z: theoretical value 684.30, measured value (M+)684.40。
Embodiment 7
With the following Isosorbide-5-Nitrae of composite structure formula, as a example by 9,12,17,20-hexa methoxy six benzos, concrete synthetic method is such as
Under:
1st, friedel-crafts acylation
In the step 1 of embodiment 3, two methyl phenyl ethers anisoles are replaced by methyl phenyl ethers anisole used by equimolar, other steps
Same as in Example 3, obtain the following clear oil compound of structural formula (2-bromophenyl) (2,5-Dimethoxyphenyl)
Ketone, its productivity is 90.8%.
2nd, boronation reaction
In the step 2 of embodiment 1,2-bromine benzophenone used equimolar (2-bromophenyl) (2,5-diformazans
Phenyl) ketone replacement, other steps are same as in Example 1, obtain the following white powdery solids of structural formula
Compound 2-(2,5-dimethoxy) Benzoylbenzene pinacol borate, its productivity is 92.3%.
3rd, coupling reaction
In the step 3 of embodiment 1,2-Benzoylbenzene pinacol borate used is with equimolar 2-(2,5-
Dimethoxy) replacement of Benzoylbenzene pinacol borate, other steps are same as in Example 1, obtain structural formula such as
Under yellow oily compound 1,3,5-tri-(((2-(2,5-dimethoxy) benzoyl) phenyl) methyl) benzene, its productivity is
88.4%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:
1HNMR (600MHz, CDCl3+ 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, CDCl3+ 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(C54H48O9) m/z: theoretical value 840.33, measured value ([M+Na]+)863.32。
4th, 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-(2,5-dimethoxy) benzoyl) phenyl) methyl) benzene is replaced, and other steps are same as in Example 1,
Obtaining the following white powdery solids compound triol of structural formula, its productivity is 99.2%.
5th, ring closure reaction
In the step 5 of embodiment 2, the triol used triol of equimolar the present embodiment step 4 gained is replaced,
Other steps are same as in Example 2, obtain yellow powdery solid compound Isosorbide-5-Nitrae, 9,12,17,20-hexa methoxy six benzene
And, its productivity is 78.2%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1H NMR (400MHz, CDCl3+ 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(C54H36O3) m/z: theoretical value 780.30,
Measured value (M+)780.10。
Embodiment 8
With the following Isosorbide-5-Nitrae of composite structure formula, as a example by 9,12,17,20-hexamethyl six benzos, concrete synthetic method is as follows:
1st, friedel-crafts acylation
In the step 1 of embodiment 1, benzene used is replaced by equimolar paraxylene, other steps and enforcement
Example 1 is identical, obtains structural formula following yellow powdery solid compound (2-bromophenyl) (2,5-3,5-dimethylphenyl) first
Ketone, its productivity is 89.6%.
2nd, boronation reaction
In the step 2 of embodiment 1,2-bromine benzophenone used equimolar (2-bromophenyl) (2,5-diformazans
Base phenyl) ketone replacement, other steps are same as in Example 1, obtain the following yellow powdery solid of structural formula
Compound 2-(2,5-dimethyl) Benzoylbenzene pinacol borate, its productivity is 90.2%.
3rd, coupling reaction
In the step 3 of embodiment 1,2-Benzoylbenzene pinacol borate used is with equimolar 2-(2,5-
Dimethyl) replacement of Benzoylbenzene pinacol borate, other steps are same as in Example 1, obtain structural formula as follows
Colorless oil compound 1,3,5-tri-(((2-(2,5-dimethyl) benzoyl) phenyl) methyl) benzene, its productivity is
83.4%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
Maxis high resolution mass spectrometer (Germany, Bruker company) characterizes, and characterizes data as follows:
1H NMR (400MHz, CDCl3+ 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)；13C NMR (100MHz, CDCl3+ 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(C54H48O3) m/z: theoretical value
744.36, measured value ([M+Na]+)767.35。
4th, 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-(2,5-dimethyl) benzoyl) phenyl) methyl) benzene is replaced, and other steps are same as in Example 1,
To the following white powdery solids compound triol of structural formula, its productivity is 97.3%.
5th, ring closure reaction
In the step 5 of embodiment 2, the triol used triol of equimolar the present embodiment step 4 gained is replaced,
Other steps are same as in Example 2, obtain yellow powdery solid compound Isosorbide-5-Nitrae, 9,12,17,20-hexamethyl six benzos
, its productivity is 55.6%.
Products therefrom with Avance type superconduction Fourier digitizing nuclear magnetic resonance spectrometer (Switzerland, Bruker company) and
MALDI-TOF mass spectrograph (Germany, Burker Daltonics) characterizes, and characterizes data as follows:
1H NMR (400MHz, CDCl3+ 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(C54H36) m/z: theoretical value 684.30,
Measured value (M+)684.50。
Claims (7)
1. the method for synthesis six vast position six benzos and derivative thereof, it is characterised in that it is by following step group
Become:
(1) friedel-crafts acylation
Be dissolved completely in bromophenyl formyl chloride in dichloromethane, 0 DEG C, add under argon shield alchlor and
Formula 1 compound, bromophenyl formyl chloride is 1:1～1.5:1～1.5 with alchlor, the mol ratio of formula 1 compound,
0 DEG C or stirring at normal temperature are reacted 2～3 hours, with saturated ammonium chloride cancellation reaction, isolated and purified product, obtain formula 2
Compound；
(2) boronation reaction
With Isosorbide-5-Nitrae-dioxane as solvent, under argon shield, by formula 2 compound, connection pinacol borate, vinegar
Acid potassium, [1,1'-double (diphenylphosphino) ferrocene] palladium chloride in molar ratio for 1:1.0～2.0:1.5～2.5:0.03～
0.1,80～100 DEG C are stirred reaction 12～24 hours, isolated and purified product, obtain formula 3 compound；
(3) coupling reaction
With Isosorbide-5-Nitrae-dioxane as solvent, under argon shield, by 1,3,5-(trisbromomethyl) benzene, formula 3 compound,
Potassium carbonate, 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, isolated and purified product, obtain formula 4 compound；
(4) reduction reaction
With dichloromethane as solvent, by formula 4 compound, methyl alcohol, sodium borohydride in molar ratio for 1:12～20:12～
20, normal-temperature reaction 1～2 hour, isolated and purified product, obtain formula 5 compound；
(5) ring closure reaction
Being dissolved completely in formula 5 compound in dichloromethane, adding TFAA and TFMS, normal temperature stirs
Mix 24～48 hours, then 0 DEG C, the nitromethane solution of dropping anhydrous ferric trichloride, dropping under argon shield
Add DDQ after complete, formula 5 compound and TFAA, TFMS, anhydrous ferric trichloride,
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
Minute, add methyl alcohol cancellation reaction, isolated and purified product, preparation six vast position six benzos shown in an accepted way of doing sth 6 or its
Derivative；
In above-mentioned formula 1～formula 6 compound, R1、R2、R3、R4Each independent representative H, C1～C4Alkyl,
C1～C4Any one in alkoxyl, phenyl.
2. the method for synthesis according to claim 1 six vast position six benzos and derivative thereof, its feature exists
In: in described formula 1～formula 6 compound, R1、R2、R3、R4Each independent representative H, methyl, methoxy
Any one in base, phenyl.
3. the method for synthesis according to claim 1 and 2 six vast position six benzos and derivative thereof, it is special
Levying and being: in described step (1), bromophenyl formyl chloride is 1:1:1.1 with alchlor, the mol ratio of formula 1 compound.
4. the method for synthesis according to claim 1 and 2 six vast position six benzos and derivative thereof, it is special
Levy and be: in described step (2), formula 2 compound and connection pinacol borate, potassium acetate, [1,1'-double (diphenyl
Phosphino-) ferrocene] mol ratio of palladium chloride is 1:1.5:2:0.05.
5. the method for synthesis according to claim 1 and 2 six vast position six benzos and derivative thereof, it is special
Levy and be: in described step (3), 1,3,5-(trisbromomethyl) benzene and formula 3 compound, potassium carbonate, four (triphenylphosphines)
The mol ratio of palladium is 1:4.5:5:0.05.
6. the method for synthesis according to claim 1 and 2 six vast position six benzos and derivative thereof, it is special
Levying and being: in described step (4), formula 4 compound is 1:18:18 with methyl alcohol, the mol ratio of sodium borohydride.
7. the method for synthesis according to claim 1 and 2 six vast position six benzos and derivative thereof, it is special
Levy and be: in described step (5), formula 5 compound and TFAA, TFMS, anhydrous ferric trichloride,
The mol ratio of DDQ is 1:9:0.9:2.4:6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510450696.2A CN105061135B (en) | 2015-07-28 | 2015-07-28 | A kind of synthesis six vast position six benzos and the method for derivative thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510450696.2A CN105061135B (en) | 2015-07-28 | 2015-07-28 | A kind of synthesis six vast position six benzos and the method for derivative thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105061135A CN105061135A (en) | 2015-11-18 |
| CN105061135B true CN105061135B (en) | 2016-11-09 |
Family
ID=54490711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510450696.2A Expired - Fee Related CN105061135B (en) | 2015-07-28 | 2015-07-28 | A kind of synthesis six vast position six benzos and the method for derivative thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061135B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129276B (en) * | 2017-12-21 | 2020-10-13 | 上海师范大学 | Preparation method of beach chair type nonabenzene compound |
| 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 |
| KR102455023B1 (en) * | 2019-12-16 | 2022-10-13 | 삼성에스디아이 주식회사 | Compound, synthesis method of the compound, hardmask composition, and method of forming patterns |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967147B (en) * | 2010-09-15 | 2012-07-04 | 陕西师范大学 | S-triazacoronene compound and synthesis method and application thereof |
| CN103265436B (en) * | 2013-05-27 | 2015-03-18 | 陕西师范大学 | Method for synthesising 1,5,9-trinitro-2,3,6,7,10,11-hexa-alkoxy triphenylene |
-
2015
- 2015-07-28 CN CN201510450696.2A patent/CN105061135B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105061135A (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105061135B (en) | A kind of synthesis six vast position six benzos and the method for derivative thereof | |
| CN104870447B (en) | Fluorescent both heterocyclic and their synthetic method | |
| CN104530105A (en) | Benzothiadiazole or benzodithiophene-bridged bis-boron-dipyrrolemethene (BODIPY) derivative organic dye and preparation method thereof | |
| CN104211599B (en) | Many alkoxyls substituted 2,3-dicarboxylic ester benzophenanthrene and preparation method thereof | |
| CN106905169B (en) | A kind of vinyl conjugation tri-arylamine group charge transport materials and preparation method thereof | |
| El Yahyaoui et al. | Convenient synthesis of photochromic symmetrical or unsymmetrical bis (heteroaryl) maleimides via the Suzuki–Miyaura cross-coupling reaction | |
| CN104974156B (en) | 1, 5, 9-triazanaphthalene coronene compound and synthetic method thereof | |
| CN109232623B (en) | Synthetic method of borazaphenanthrene and derivatives thereof | |
| CN115304618B (en) | Chiral thiophene spiroalkene based on triptycene and preparation method thereof | |
| Li et al. | The unprecedented C-alkylation and tandem C-/O-alkylation of phenanthrolinium salts with cyclic 1, 3-dicarbonyl compounds | |
| CN105713003B (en) | π extends equal San Dan Za guans derivatives and its synthetic method | |
| CN106632440B (en) | A kind of preparation method of aryl-boric acid ester and ene boric acid ester | |
| CN115650951A (en) | Diaryl ethylene organic photochromic material and preparation method thereof | |
| CN103554023A (en) | Synthesis method of acridine derivative and synthesized polycyclic acridine derivative | |
| CN115353529A (en) | Chiral spiro compound, preparation method and application thereof | |
| Zhang et al. | Synthesis and characterization of pyrimidine-containing hexaarylbenzene derivatives | |
| CN109111351A (en) | A kind of synthetic method of asymmetry 9- alkoxy phenanthrene dimer | |
| CN105176518A (en) | Dithienopyridine zinc coordination compound luminescence material and preparation method thereof | |
| CN108558595B (en) | P-phenylene ethylene bridged trimer indene derivative and preparation method thereof | |
| CN106045836A (en) | Method for synthesizing aromatic hydrocarbon or heterocyclic trifluoromethylketone under catalytic action of copper | |
| Hu et al. | Synthesis of N, O π-conjugated boron complexes and the reactivity of Suzuki cross-coupling | |
| CN104628753A (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
| Zhang | Synthesis of Diarylmethanes via Pd-Catalyzed Coupling of Aryltosylates with Benzyltitanium Reagents | |
| CN109232169A (en) | A kind of polyaryl replaces fulvalene compound and its synthetic method | |
| CN105016988B (en) | Polyalkyloxy substituted 1,2-benzochrysene derivative and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161109 Termination date: 20200728 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |