CN107266411A - A kind of synthetic method of 9,10 Benzophenanthrene compound - Google Patents
A kind of synthetic method of 9,10 Benzophenanthrene compound Download PDFInfo
- Publication number
- CN107266411A CN107266411A CN201710554345.5A CN201710554345A CN107266411A CN 107266411 A CN107266411 A CN 107266411A CN 201710554345 A CN201710554345 A CN 201710554345A CN 107266411 A CN107266411 A CN 107266411A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound shown
- compound
- reaction
- alkoxy
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/28—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by ring closure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of synthetic method of 9,10 Benzophenanthrene compounds, it includes the step shown in following reaction equation, is specially：Under inert gas shielding; the compound shown in compound and formula (4) shown in formula (2) is dissolved in N; in N dimethylformamides and in the presence of copper trifluoromethanesulfcomposite, sodium carbonate and cesium acetate; 9,10 Benzophenanthrene compounds shown in formula (I) are obtained in 120~140 DEG C of reactions；
Description
Technical field
The present invention relates to the synthesis technical field of organic compound, and in particular to one kind 9,10- Benzophenanthrene compounds
Synthetic method.
Background technology
Into 21 century, with functional material, it is biomedical in terms of fast development, with having for big pi-conjugated system
Machine functional material has very many applications in fields such as photoelectricity.Condensed-nuclei aromatics (PAH) is used as a kind of typical big pi-conjugated system
Compound, can control some functional materials in the key performance of photoelectric field.In condensed-nuclei aromatics, 9,10- benzophenanthrene conducts
Minimum graphite alkene monomer, its synthetic method also receives the attention of many scientists in the whole world.Synthesis benzophenanthrene has many at present
Kind of method, but it is more all to there is synthesis step, and the deficiency such as condition harshness.
The content of the invention
Therefore, it is for synthesizing the more method and step of benzophenanthrene and harsh condition in the prior art the problem of, of the invention
Purpose is the provision of a kind of synthetic method of 9, the 10- Benzophenanthrene compounds using diaryl group iodized salt as aromatic yl reagent-ing.
The synthetic method of 9, the 10- Benzophenanthrene compounds of the present invention includes the step shown in following reaction equation, is specially：
Under inert gas (such as nitrogen, argon gas etc.) protection, the compound shown in compound and formula (4) shown in formula (2) is dissolved in N, N-
In dimethylformamide (DMF) and in the presence of copper trifluoromethanesulfcomposite, sodium carbonate and cesium acetate, in 120~140 DEG C preferably
130 DEG C of reactions obtain the 9,10- Benzophenanthrene compounds shown in formula (I)；
In compound shown in formula (2), R1Selected from hydrogen, C1~18Alkyl, C1~8Alkoxy, C6~20Aromatic radical, hydroxyl, fluorine,
Chlorine, bromine, nitro, trifluoromethyl, cyano group, formoxyl, acetyl group and C1~8One or two in alkoxy carbonyl group；R1Residing
Position on phenyl ring can arbitrarily be selected, such as R1During for a substituent, ortho position, meta or para position, R can be located at1For two substitutions
During base, ortho position and meta, ortho position and contraposition, meta and meta or meta and contraposition can be located at respectively；
In compound shown in formula (4), R2Selected from hydrogen, C1~18Alkyl, C1~8Alkoxy, C6~20Aromatic radical, fluorine, chlorine and bromine
In one；R3Selected from hydrogen, C1~18Alkyl, C1~8Alkoxy, C6~20One, two or three in aromatic radical, fluorine, chlorine and bromine；
R2And R3The position on residing phenyl ring can arbitrarily be selected respectively, such as R2Ortho position, meta or para position can be located at；R3For one
During substituent, ortho position, meta or para position may be alternatively located at；R3During for two substituents, can be located at respectively ortho position and meta, ortho position and
Contraposition, meta and meta or meta and contraposition；R3During for three substituents, the position of substituent also can arbitrarily be selected, preferably
Two ortho positions and contraposition；
Above-mentioned C1~18Alkyl can be that straight chained alkyl can also be branched alkyl when carbon number is more than or equal to 3；
C1~18The C such as the preferred methyl of alkyl, ethyl, propyl group, butyl, isobutyl group, the tert-butyl group1~4Alkyl；
Above-mentioned C1~8Alkoxy can be that unbranched alkoxy can also be side chain alcoxyl when carbon number is more than or equal to 3
Base；C1~8The C such as the preferred methoxyl group of alkoxy, ethyoxyl, propoxyl group, n-butoxy, isobutoxy, tert-butoxy1~4Alkoxy.
Above-mentioned C1~8Alkoxy carbonyl group can be that straight chain alkoxy carbonyl group can also be side chain when carbon number is more than or equal to 4
Alkoxy carbonyl group；C1~8The preferred methoxycarbonyl group of alkoxy carbonyl group, carbethoxyl group, propylene carbonyl oxygen, positive butoxy carbonyl, isobutyl boc, tertiary fourth
The C such as oxygen carbonyl1~4Alkoxy carbonyl group；
Above-mentioned C6~20Aromatic radical refers to monocyclic, polycyclic aromatic group with 6-20 carbon atom, representational aryl bag
Include phenyl, naphthyl etc.；
R1、R2And R3In, C1~18Alkyl, C1~8Alkoxy, C6~20Aromatic radical, formoxyl, acetyl group and C1~8Alkoxy carbonyl group
Can be it is unsubstituted, can also be by C1~8Alkyl, halogen or methoxyl group etc. replace.
Preferably, on the basis of the mole that feeds intake of the compound shown in formula (2), compound shown in formula (4) for 1.2~
2.0 equivalents, preferably 1.5 equivalents；Copper trifluoromethanesulfcomposite is 0.05~0.2 equivalent, preferably 0.1 equivalent；Sodium carbonate is 1.5
~3 equivalents, preferably 2 equivalents；Cesium acetate is 2~4 equivalents, preferably 3 equivalents.
The compound shown in compound and formula (4) shown in formula (2) generally can be anti-in 8~16 hours at 120~140 DEG C
Should be complete.
In some preferred embodiments of the present invention, in the compound shown in formula (2), R1Selected from hydrogen, methyl, ethyl, methoxy
One in base, ethyoxyl, nitro, trifluoromethyl, cyano group, fluorine, chlorine and bromine, or selected from methyl, ethyl, methoxyl group and ethyoxyl
In two and respectively be located at meta and contraposition.
Compound shown in formula (2) can be made by following reaction equation, be specially：Compound and adjacent bromine shown in formula (1)
Iodobenzene is coupled the compound obtained shown in formula (2) in the presence of palladium catalyst and inorganic base；
In compound shown in formula (1), R1It is defined as previously described.
Compound shown in formula (1) can be bought directly from market, or pass through the normal of phenyl boric acid by commercially available substituted phenyl-bromide
Regulation Preparation Method is made.
Preferably, when the compound shown in formula (1) is coupled with adjacent bromo-iodobenzene, solvent is the glycol dimethyl ether of mixing
(DME) and water, inorganic base is potassium carbonate, and palladium catalyst is two triphenylphosphine palladiums, reaction temperature be 75~90 DEG C preferably
80℃；On the basis of the mole that feeds intake of the compound shown in formula (1), adjacent bromo-iodobenzene is that 1.2~2 equivalents preferably 1.5 are worked as
Amount, potassium carbonate is preferably 1.5 equivalents of 1.2~2 equivalents, and two triphenylphosphine palladiums are that 0.01~0.03 equivalent is preferred
0.02 equivalent.
Some preferred embodiments of the present invention are as follows：
Above in various shown compound, R1One in foregoing group.In addition, formula (1D), (2D)
In (I D), two R1It is separate, you can be identical group or different group.
In some preferred embodiments of the present invention, the R in compound shown in formula (4)2And R3It is identical.Such as, R2And R3
For hydrogen, or it is the methyl positioned at contraposition, ethyl, isopropyl, methoxy or ethoxy.
In other preferred embodiments of the present invention, the R in compound shown in formula (4)2And R3Difference, wherein, R2For hydrogen
Or the methyl positioned at contraposition, ethyl, isopropyl, methoxy or ethoxy；R3It is located at the methyl at ortho position and contraposition respectively for three
Or ethyl.
Compound shown in formula (4) is the diphenyl iodnium of trifluoromethanesulfonic acid anion, works as R2And R3When identical, it can pass through
It is prepared by following steps：By R2Substituted benzene, iodine, metachloroperbenzoic acid are dissolved in dichloromethane, then trifluoro are added dropwise
Solvent is spin-dried for by methanesulfonic acid, reaction after 1~2 hour, is added absolute ether precipitation crystal and is produced shown in formula (4A) or formula (4B)
Compound.And work as R2And R3Also need to add R when different, when feeding intake in above-mentioned steps3Substituted benzene, with R2Substituted benzene is simultaneously
It is used as reaction substrate, R3The trimethyl toluene of substituted benzene preferably 1,3,5-, can be made formula (4A ') or the compound shown in (4B '),
It is effectively reduced the accessory substance of the step and follow-up arylation step.
In compound shown in formula (4A), (4B), (4A ') and (4B '), R2One in foregoing group.
Other formula (two R in the compound shown in (4B) and (4B ')2It is separate, you can be identical group or not
Same group.
The positive effect of the present invention is：The synthetic method of 9,10- Benzophenanthrene compounds disclosed by the invention is
With 2- bromo biphenyls (compound shown in formula (2)) for raw material, diaryl group iodized salt (compound shown in formula (4)) is tried as arylation
Agent, cupric is as catalyst, and sodium carbonate and cesium acetate are as mixed base, and reaction obtains 9,10- at 120~140 DEG C in DMF
Benzophenanthrene compound.This method has raw material is relative to be easy to get, and the reaction time is shorter, the features such as yield is higher, and synthesizes
9, the 10- Benzophenanthrene compounds arrived have preferably as a kind of graphite alkene monomer the simplest in fields such as organic photoelectrics
Application prospect.
Embodiment
In order to further illustrate the present invention, following serial specific embodiment is provided, but the present invention is not specific real by these
The limitation of example is applied, any understanding person skilled in art will can reach similar result to the few modifications of the present invention, this
A little change is also contained among the present invention.
Embodiment 1
By phenyl boric acid (1a, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two triphenylphosphines two
Palladium bichloride (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, at the same add 30mL DME (glycol dimethyl ether) and
6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.After reaction terminates, it is cooled to
Room temperature, adds 50mL water quenchings and goes out reaction, extracted three times with 100mL ethyl acetate, organic phase anhydrous sodium sulfate drying, filtering is revolved
Dry column chromatography separating-purifying (eluent：PE compound 2a) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv), is used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2a (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3aa (yield 72%)) is obtained.
3aa：White solid；198-199 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.69-8.64(m,6H),7.70-
7.65(m,6H)；13C NMR(100MHz,CDCl3):δ129.8,127.2,123.3.
Embodiment 2
By 4- methylphenylboronic acids (1b, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two triphens
Base phosphine dichloride palladium (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mLDME (glycol dinitrates
Ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.After reaction terminates,
It is cooled to room temperature, adds 50mL water quenchings and go out reaction, with 100mL ethyl acetate extraction three times, organic phase anhydrous sodium sulfate drying,
Filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2b) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2b (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ab (yield 63%)) is obtained.
3ab：White solid；101-102 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.68-8.62(m,4H),8.54
(d, J=8.4Hz, 1H), 8.45 (s, 1H), 7.69-7.63 (m, 4H), 7.49 (dd, J=8.4,1.2Hz, 1H), 2.62 (s,
3H)；13C NMR(100MHz,CDCl3)δ136.9,129.9,129.8,129.8,129.7,129.4,128.7,127.5,
127.2,127.2,127.1,127.1,126.8,123.3,123.3,123.1,21.9.
Embodiment 3
By 2- methylphenylboronic acids (1c, 12mmol, 1.2eeqquiv) and potassium carbonate (15mmol, 1.5equiv) and two or three
Phenylphosphine palladium chloride (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mL DME (ethylene glycol
Dimethyl ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.Reaction terminates
Afterwards, it is cooled to room temperature, adds 50mL water quenchings and go out reaction, extracted three times with 100mL ethyl acetate, organic phase is done with anhydrous sodium sulfate
Dry, filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2c) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2c (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ac (yield 61%)) is obtained.
3ac：White solid；94-96 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ 8.65 (dd, J=8.0,1.6Hz,
1H), 8.63-8.59 (m, 3H), 8.54 (dd, J=7.6,1.6Hz, 1H), 7.68-7.51 (m, 6H), 3.07 (s, 3H)；13C
NMR(100MHz,CDCl3)δ135.4,131.6,131.3,131.0,130.7,130.4,129.9,128.5,127.3,
127.1,126.6,126.3,125.6,123.6,123.2,123.0,121.0,26.7.
Embodiment 4
By 3,4- dimethylphenyl boronic acids (1d, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two
Triphenylphosphine palladium (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mLDME (ethylene glycol
Dimethyl ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.Reaction terminates
Afterwards, it is cooled to room temperature, adds 50mL water quenchings and go out reaction, extracted three times with 100mL ethyl acetate, organic phase is done with anhydrous sodium sulfate
Dry, filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2d) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2d (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ad (yield 36%)) is obtained.
3ad：White solid；156-157 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.65-8.62(m,4H),8.40
(s,2H),7.66-7.60(m,4H),2.53(s,6H)；13C NMR(100MHz,CDCl3)δ136.2,129.8,129.5,
127.9,127.0,126.6,123.9,123.2,123.0,20.3.
Embodiment 5
By 4- fluorobenzoic boric acids (1e, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two triphenyls
Phosphine dichloride palladium (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mL DME (glycol dinitrates
Ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.After reaction terminates,
It is cooled to room temperature, adds 50mL water quenchings and go out reaction, with 100mL ethyl acetate extraction three times, organic phase anhydrous sodium sulfate drying,
Filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2e) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2e (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ae (yield 55%)) is obtained.
3ae：White solid；188-189 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.65-8.53(m,4H),8.51-
8.47 (m, 1H), 8.24 (dd, J=11.2,2.8Hz, 1H), 7.71-7.62 (m, 4H), 7.37 (ddd, J=9.1,7.8,
2.6Hz,1H)；13C NMR(100MHz,CDCl3) δ 162.2 (d, J=244.0Hz), 131.8 (d, J=8.0Hz), 130.2,
(d, J=3.3Hz), 129.3,129.3,129.0 127.9,127.4,127.3,127.1,126.3 (d, J=2.2Hz), 125.6
(d, J=8.7Hz), 123.5,123.4,123.4,123.1,115.4 (d, J=22.7Hz), 108.8 (d, J=22.2Hz)；19F
NMR(376MHz,CDCl3):δ-114.15(s,1F).
Embodiment 6
By 4- methoxyphenylboronic acids (1f, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two or three
Phenylphosphine palladium chloride (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mL DME (ethylene glycol
Dimethyl ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.Reaction terminates
Afterwards, it is cooled to room temperature, adds 50mL water quenchings and go out reaction, extracted three times with 100mL ethyl acetate, organic phase is done with anhydrous sodium sulfate
Dry, filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2f) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2f (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3af (yield 80%)) is obtained.
3af：White solid；101-102 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.67-8.62(m,2H),8.60-
8.54 (m, 3H), 8.05 (d, J=2.4Hz, 1H), 7.69-7.58 (m, 4H), 7.28 (dd, J=9.2,2.8Hz, 1H), 4.03
(s,3H)；13C NMR(100MHz,CDCl3)δ158.9,131.3,130.2,129.9,129.5,128.8,127.3,127.3,
127.1,126.3,125.0,123.8,123.4,123.3,123.3,122.8,115.8,105.8,55.5.
Embodiment 7
By 4- nitrobenzene boronic acids (1g, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two triphens
Base phosphine dichloride palladium (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mL DME (ethylene glycol two
Methyl ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.Reaction terminates
Afterwards, it is cooled to room temperature, adds 50mL water quenchings and go out reaction, extracted three times with 100mL ethyl acetate, organic phase is done with anhydrous sodium sulfate
Dry, filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2g) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2g (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ag (yield 88%)) is obtained
3ag：White solid；158-159 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ 9.33 (d, J=2.4Hz, 1H),
8.61-8.50 (m, 5H), 8.30 (dd, J=9.2,2.4Hz, 1H), 7.76-7.65 (m, 4H)；13C NMR(100MHz,CDCl3)
δ146.3,134.3,131.0,130.1,130.0,129.2,128.6,128.6,128.1,127.9,127.7,124.4,
124.2,123.5,123.4,120.8,119.1.
Embodiment 8
By 4- trifluoromethylbenzene boronic acids (1h, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two
Triphenylphosphine palladium (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mLDME (ethylene glycol
Dimethyl ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.Reaction terminates
Afterwards, it is cooled to room temperature, adds 50mL water quenchings and go out reaction, extracted three times with 100mL ethyl acetate, organic phase is done with anhydrous sodium sulfate
Dry, filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2h) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2h (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ah (yield 87%)) is obtained.
3ah：White solid；109-111 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ 8.89 (s, 1H), 8.73 (d, J=
8.8Hz, 1H), 8.68-8.63 (m, 4H), 7.85 (dd, J=8.8,1.6Hz, 1H), 7.76-7.67 (m, 4H)；13C NMR
(100MHz,CDCl3) δ 132.2 (d, J=0.9Hz), 130.4,130.0,129.6,129.0,128.7,128.3,128.1,
(127.6,127.5,124.1,123.7,123.4,123.4,123.4,123.2 q, J=3.1Hz), 120.60 (q, J=
4.4Hz)；19F NMR(376MHz,CDCl3):δ-62.01(s,3F).
Embodiment 9
By 4- cyanophenylboronic acids (1i, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two triphens
Base phosphine dichloride palladium (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mL DME (ethylene glycol two
Methyl ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.Reaction terminates
Afterwards, it is cooled to room temperature, adds 50mL water quenchings and go out reaction, extracted three times with 100mL ethyl acetate, organic phase is done with anhydrous sodium sulfate
Dry, filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2i) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2i (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ai (81%)) is obtained.
3ai：White solid；215-216 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ 8.89 (d, J=1.6Hz, 1H),
8.67-8.62 (m, 3H), 8.59 (dd, J=8.0,1.2Hz, 1H), 8.56-8.52 (m, 1H), 7.81 (dd, J=8.8,
1.6Hz,1H),7.77-7.67(m,4H)；13C NMR(100MHz,CDCl3)δ132.9,130.8,130.1,129.9,128.9,
128.9,128.4,128.3,128.3,128.1,127.9,127.7,124.2,123.9,123.5,123.5,123.2,
119.4,110.5.
Embodiment 10
By 3- chlorophenylboronic acids (1j, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and two triphenyls
Phosphine dichloride palladium (0.2mmol, 0.02equiv) is placed in 100mL round-bottomed flasks, while adding 30mL DME (glycol dinitrates
Ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.After reaction terminates,
It is cooled to room temperature, adds 50mL water quenchings and go out reaction, with 100mL ethyl acetate extraction three times, organic phase anhydrous sodium sulfate drying,
Filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2j) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2j (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3aj (yield 36%)) is obtained.
3aj：White solid；145-146 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.64-8.61(m,2H),8.58-
8.52 (m, 4H), 7.71-7.63 (m, 4H), 7.58 (dd, J=8.8,2.0Hz, 1H)；13C NMR(100MHz,CDCl3)δ
133.3,131.2,130.1,129.6,129.1,128.6,128.2,127.8,127.5,127.4,127.4,124.9,
123.3,123.2,123.0.
Embodiment 11
By 3,4- dimethoxyphenylboronics (1k, 12mmol, 1.2equiv) and potassium carbonate (15mmol, 1.5equiv) and
Two triphenylphosphine palladiums (0.2mmol, 0.02equiv) are placed in 100mL round-bottomed flasks, while adding 30mLDME (second two
Diethylene glycol dimethyl ether) and 6mL H2O, adds adjacent bromo-iodobenzene (10mmol, 1.0equiv), is heated to 80 DEG C and reacts 6 hours.Reaction knot
Shu Hou, is cooled to room temperature, adds 50mL water quenchings and goes out reaction, with 100mL ethyl acetate extraction three times, organic phase anhydrous sodium sulfate
Dry, filtering is spin-dried for pillar layer separation purification (eluent：PE compound 2k) is obtained.
N2Under protection, diaryl group iodized salt (0.3mmol, 1.5equiv), Cu are sequentially added in 25mL Schlenk bottles
(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv) are used
Syringe is added to react 12 hours at the heavy steamed DMF of reaction substrate 2k (0.2mmol, 1.0equiv) and 4mL, 130 DEG C.Reaction
After end, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3ak (yield 59%)) is obtained.
3ak：White solid；164-165 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.68-8.65(m,2H),8.52-
8.49(m,2H),8.00(s,2H),7.68-7.59(m,4H),4.13(s,6H)；13C NMR(100MHz,CDCl3)δ149.4,
129.5,129.2,127.0,126.3,124.2,123.4,122.8,104.5,56.0.
Embodiment 12
N2Under protection, dimethoxy base salt compounded of iodine (0.3mmol, 1.5equiv) is sequentially added in 25mL Schlenk bottles,
Cu(OTf)2(0.01mmol, 3.61mg), Na2CO3(0.4mmol, 2.0equiv) and CsOAc (0.6mmol, 3.0equiv)
Added and reacted 12 hours at the heavy steamed DMF of reaction substrate 2a (0.2mmol, 1.0equiv) and 4mL, 130 DEG C with syringe.Instead
After should terminating, solvent is spin-dried for, dry method loading crosses post separation purification (eluent：PE target product 3af (yield 90%)) is obtained.
3af：White solid；101-102 DEG C of fusing point；1H NMR(400MHz,CDCl3):δ8.67-8.62(m,2H),8.60-
8.54 (m, 3H), 8.05 (d, J=2.4Hz, 1H), 7.69-7.58 (m, 4H), 7.28 (dd, J=9.2,2.8Hz, 1H), 4.03
(s,3H)；13C NMR(100MHz,CDCl3)δ158.9,131.3,130.2,129.9,129.5,128.8,127.3,127.3,
127.1,126.3,125.0,123.8,123.4,123.3,123.3,122.8,115.8,105.8,55.5。
Claims (10)
1. one kind 9, the synthetic method of 10- Benzophenanthrene compounds, it is characterised in that it includes the step shown in following reaction equation
Suddenly, it is specially：Under inert gas shielding, the compound shown in compound and formula (4) shown in formula (2) is dissolved in N, N- dimethyl methyls
In acid amides and in the presence of copper trifluoromethanesulfcomposite, sodium carbonate and cesium acetate, obtained in 120~140 DEG C of reactions shown in formula (I)
9,10- Benzophenanthrene compounds；
In compound shown in formula (2), R1Selected from hydrogen, C1~18Alkyl, C1~8Alkoxy, C6~20Aromatic radical, hydroxyl, fluorine, chlorine, bromine,
Nitro, trifluoromethyl, cyano group, formoxyl, acetyl group and C1~8One or two in alkoxy carbonyl group；
In compound shown in formula (4), R2Selected from hydrogen, C1~18Alkyl, C1~8Alkoxy, C6~20In aromatic radical, fluorine, chlorine and bromine
One；R3Selected from hydrogen, C1~18Alkyl, C1~8Alkoxy, C6~20One, two or three in aromatic radical, fluorine, chlorine and bromine；
R1、R2And R3In, C1~18Alkyl, C1~8Alkoxy, C6~20Aromatic radical, formoxyl, acetyl group and C1~8Alkoxy carbonyl group is not take
Generation or by C1~8Alkyl, halogen or methoxy substitution.
2. the method as described in claim 1, it is characterised in that on the basis of the mole that feeds intake of the compound shown in formula (2),
Compound shown in formula (4) is 1.2~2.0 equivalents, copper trifluoromethanesulfcomposite be 0.05~0.2 equivalent, sodium carbonate be 1.5~
3 equivalents, cesium acetate is 2~4 equivalents.
3. the method as described in claim 1, it is characterised in that in the compound shown in formula (2), R1Selected from hydrogen, methyl, ethyl,
One in methoxyl group, ethyoxyl, nitro, trifluoromethyl, cyano group, fluorine, chlorine and bromine.
4. the method as described in claim 1, it is characterised in that in the compound shown in formula (2), R1Selected from methyl, ethyl, first
Two in epoxide and ethyoxyl and it is located at meta and contraposition respectively.
5. the method as described in any one of Claims 1 to 4, it is characterised in that it also includes the compound shown in formula (2)
The step of, reaction equation is as follows, is specially：The effect of compound shown in formula (1) and adjacent bromo-iodobenzene in palladium catalyst and inorganic base
Lower coupling obtains the compound shown in formula (2)；
In compound shown in formula (1), R1Definition as described in any one of Claims 1 to 4.
6. method as claimed in claim 5, it is characterised in that when the compound shown in formula (1) is coupled with adjacent bromo-iodobenzene, solvent
For the glycol dimethyl ether and water of mixing, inorganic base is potassium carbonate, and palladium catalyst is two triphenylphosphine palladiums, reaction temperature
For 75~90 DEG C；On the basis of the mole that feeds intake of the compound shown in formula (1), adjacent bromo-iodobenzene is 1.2~2 equivalents, carbonic acid
Potassium is 1.2~2 equivalents, and two triphenylphosphine palladiums are 0.01~0.03 equivalent.
7. the method as described in claim 1, it is characterised in that in the compound shown in formula (4), R2And R3It is identical.
8. method as claimed in claim 7, it is characterised in that in the compound shown in formula (4), R2And R3It is hydrogen, or is
Positioned at the methyl of contraposition, ethyl, isopropyl, methoxy or ethoxy.
9. the method as described in claim 1, it is characterised in that in the compound shown in formula (4), R2For hydrogen or positioned at contraposition
Methyl, ethyl, isopropyl, methoxy or ethoxy；R3It is located at the methyl or ethyl at ortho position and contraposition respectively for three.
10. method as claimed in claim 7, it is characterised in that the step of it also includes the compound shown in formula (4),
Specially：By R2Substituted benzene, iodine, metachloroperbenzoic acid are dissolved in dichloromethane, then are added dropwise trifluoromethanesulfonic acid,
Solvent is spin-dried for by reaction after 1~2 hour, and addition absolute ether precipitation crystal produces the compound shown in formula (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710554345.5A CN107266411B (en) | 2017-07-07 | 2017-07-07 | A kind of synthetic method of 9,10- Benzophenanthrene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710554345.5A CN107266411B (en) | 2017-07-07 | 2017-07-07 | A kind of synthetic method of 9,10- Benzophenanthrene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107266411A true CN107266411A (en) | 2017-10-20 |
| CN107266411B CN107266411B (en) | 2019-06-28 |
Family
ID=60072511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710554345.5A Active CN107266411B (en) | 2017-07-07 | 2017-07-07 | A kind of synthetic method of 9,10- Benzophenanthrene compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107266411B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041165A (en) * | 2019-05-10 | 2019-07-23 | 安徽秀朗新材料科技有限公司 | A kind of preparation method of 2- bromine triphenylene |
| CN111675591A (en) * | 2020-06-28 | 2020-09-18 | 安徽师范大学 | Synthetic method of benzophenanthrene compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102224121A (en) * | 2008-11-25 | 2011-10-19 | 阿尔比马尔公司 | Processes for preparing triphenylene |
| CN103012047A (en) * | 2013-01-10 | 2013-04-03 | 常州南京大学高新技术研究院 | Simple synthesis method of benzophenanthrene |
-
2017
- 2017-07-07 CN CN201710554345.5A patent/CN107266411B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102224121A (en) * | 2008-11-25 | 2011-10-19 | 阿尔比马尔公司 | Processes for preparing triphenylene |
| CN103012047A (en) * | 2013-01-10 | 2013-04-03 | 常州南京大学高新技术研究院 | Simple synthesis method of benzophenanthrene |
Non-Patent Citations (1)
| Title |
|---|
| 肖志超等: "二芳基碘鎓盐在有机反应中的研究新进展", 《有机化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041165A (en) * | 2019-05-10 | 2019-07-23 | 安徽秀朗新材料科技有限公司 | A kind of preparation method of 2- bromine triphenylene |
| CN111675591A (en) * | 2020-06-28 | 2020-09-18 | 安徽师范大学 | Synthetic method of benzophenanthrene compound |
| CN111675591B (en) * | 2020-06-28 | 2022-09-30 | 安徽师范大学 | Synthetic method of benzophenanthrene compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107266411B (en) | 2019-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107501156B (en) | Three-component series synthesis method of polysubstituted pyrrole | |
| CN107266411A (en) | A kind of synthetic method of 9,10 Benzophenanthrene compound | |
| KR101067069B1 (en) | Process for preparing phenanthridine derivatives using trifluoroacetic acid | |
| CN108822035B (en) | Preparation method of 4-substituted thiophenyl isoquinoline-1 (2H) -ketone compound | |
| CN108586519A (en) | A kind of preparation method of organosilan or organic germanium alkane derivatives | |
| CN104046351B (en) | There is the luminous organic material of afterglow performance and synthetic method thereof and application | |
| CN108864164B (en) | Synthesis method of primary amine-guided 2-alkynyl indole compound | |
| CN108047128A (en) | A kind of method for synthesizing (E) -2- methyl 4-phenyl -6- styryl substituted pyridine compounds | |
| WO2016141826A1 (en) | Method for synthesising pharmaceutical intermediate phenanthrene compound in potassium tert-butoxide environment | |
| CN103030627B (en) | A kind of synthetic method of thiphene ring/furan nucleus Heteroaryl ring structures | |
| CN105481738B (en) | A kind of method of the copper catalysis synthesis trifluoroethyl thioether of aromatic hydrocarbons 2,2,2 | |
| CN106632213B (en) | A kind of synthetic method of dibenzopyrans coupling compound | |
| CN110041176B (en) | Preparation method of thermosensitive paper sensitizer ethylene glycol diphenyl ether | |
| CN104496881A (en) | Preparation method for synthesizing indoline from amide compounds by catalysis of copper salt | |
| CN110407830A (en) | A method of synthesis N- aryl phenothiazine compound | |
| CN105712956B (en) | A kind of preparation method of gentle efficient polyfunctional group substituted epoxy class compound | |
| CN109988113A (en) | A kind of synthetic method of [60] fullerene tetrahydroquinoline derivative | |
| CN109020922B (en) | Preparation method of cyclic sulfonamide compound | |
| CN109912640A (en) | A kind of preparation method of 2-Pyrrolidone class compound | |
| CN110105259B (en) | Method for removing sulfinyl in heteroarene compound | |
| CN107663165A (en) | The new method that a kind of C H bond activations of the positions of indoles C 3 are efficiently esterified | |
| CN106588651A (en) | Styrenic quaternary carbon compound and preparation method thereof | |
| CN107739379A (en) | A kind of imidazoles [1,2 a:3,4 a '] and two pyridine salt compounds synthetic method | |
| CN110577483B (en) | Green synthesis method of 3, 3-disubstituted-2-indolone | |
| CN106565603A (en) | Method for synthesizing 5,7-binitro-8-carboxamidoquinoline compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |