CN108586342A - Condensed biaryl azatropylidene -5- ketone compounds and its synthetic method - Google Patents
Condensed biaryl azatropylidene -5- ketone compounds and its synthetic method Download PDFInfo
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Abstract
The present invention is a kind of 5 ketone compounds synthetic method of condensed biaryl azatropylidene：This method is that ruthenium, palladium catalyst are catalyzed aryl methanol altogether and hydrogen transfer reaction occurs for aryl cyanides and carbon-hydrogen bond activation reacts a step and generates biaryl and 5 ketone compounds of azatropylidene.The preparation process of such compound is：Aryl methanol and aryl cyanides, ruthenium catalyst, palladium salt, azacyclo- imidazole salts, silver oxide and alkali is taken to be added in organic solvent, in N2It is heated under gas shielded, filters, is evaporated after reaction, recrystallizing up to product.Ruthenium, palladium catalyst are simple and easy to get used in the method for the present invention, and the cheap range of reaction substrate is wide, economical in reaction is efficient, is conducive to industrialized production.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to the condensed biaryl azatropylidene -5- ketone compounds of one kind, and
The synthetic method of such compound.
Background technology
The basic structural unit of azatropylidene class compound is seven yuan of Zhuo Huan containing a nitrogen-atoms, aryl and azatropylidene class
It is the heterocyclic compound for having unique physiological activity and pharmacological activity to close object, receives the concern of people.Some of compounds
The effect of with antipsychotic disease, analgesic and treatment cardiovascular disease etc., there are prodigious pharmaceutical potential and wide application
Foreground.Although the aryl and azatropylidene class compound now with many types are synthesized, biaryl and azatropylidene-are condensed
The also rare report of 5- ketone compounds.Existing synthetic method needs to use special substrate, is not easy to obtain and type is limited, system
It is standby relatively complicated, it is expensive, it is also needed in addition with to the unfavorable Phosphine ligands of environment, environmental pollution is big, makes them in industry
Certain limitation is received in production.
In recent years, the hydrogen transfer reaction of metal catalytic alcohol and carbon-hydrogen bond activation reaction, it has also become carbon-carbon bond generates important
An indispensable means in method and organic synthesis.We are catalyzed adjacent halogen aryl methanol and virtue by ruthenium, palladium catalyst altogether
Hydrogen transfer reaction occurs for base formonitrile HCN and carbon-hydrogen bond activation reaction one-step synthesis condenses biaryl azatropylidene -5- ketone compounds, instead
Answer substrate alcohol cheap and easily-available, environmentally friendly, used catalyst commodity can obtain, and economical in reaction is efficient, be conducive to industrialized production,
It has a extensive future.
Invention content
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of new condensed biaryl
Azatropylidene -5- ketone compounds.
There is provided the preparation methods of aforesaid compound for another technical problem to be solved by this invention.
Based on above-mentioned purpose, present invention employs following technical solutions：The present invention is a kind of condensed biaryl azatropylidene -5-
Ketone compounds, its main feature is that, the structural formula such as (II) of the condensed biaryl azatropylidene -5- ketone compounds is shown：
R1、R2Selected from-H ,-CH3、-CF3、-OCH3、-C2H5、-OC2H5、-C6H5、-CH2C6H5、-NO2、-COCH3、-
COOCH3、-CHO、-F、-Cl、-Br；R1In aromatic ring 1-4, R2Any position on aromatic ring 8-11.
The invention also discloses a kind of preparation method of condensed biaryl azatropylidene -5- ketone compounds as described above,
Aryl methanol and aryl cyanides, ruthenium catalyst, palladium salt, azacyclo- imidazole salts, silver oxide and alkali is taken to be added in organic solvent,
N2It is heated under gas shielded, processing after reaction obtains the condensed biaryl azatropylidene -5- ketone compounds.
The preparation method route of condensed biaryl azatropylidene -5- ketone compounds is as follows：
The structural formula of the aryl methanol and aryl cyanides is such as shown in (I)：
The structural formula of the condensed biaryl azatropylidene -5- ketone compounds is such as shown in (II)：
The R of the aryl methanol and aryl cyanides1、R2In group and condensed union II aryl azatropylidene -5- ketone compounds
R1、R2Group connotation is identical.In wherein (I)~(II)：R1、R2It may each be-H ,-CH3、-CF3、-OCH3、-C2H5、-OC2H5、-
C6H5、-CH2C6H5、-NO2、-COCH3、-COOCH3、-CHO、-F、-Cl、-Br；R1It can be in aromatic ring 1-4, R2It can be in aromatic ring 8-
Any position on 11.
The preparation method of the condensed biaryl azatropylidene -5- ketone compounds, further preferred technical solution are：
The ruthenium catalyst is RuH2(PPh3)4、RuH2(CO)(PPh3)3.Palladium salt is palladium bichloride, palladium.
The preparation method of the condensed biaryl azatropylidene -5- ketone compounds, further preferred technical solution are：
The azacyclo- imidazole salts are bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of 1,3-, 1,3- bis- (2,6- diisopropyl phenyls)
Limidazolium, 1,3- bis- (2,6- diisopropylbenzyl) -4,5- glyoxalidine tetrafluoroborates.
The preparation method of the condensed biaryl azatropylidene -5- ketone compounds, further preferred technical solution are：
The alkali is sodium hydride, sodium tert-butoxide, potassium tert-butoxide.
The preparation method of the condensed biaryl azatropylidene -5- ketone compounds, further preferred technical solution are：
The organic solvent is benzene, toluene, dioxane, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO).
The preparation method of the condensed biaryl azatropylidene -5- ketone compounds, further preferred technical solution are：
Neighbour's halogen aryl methanol and aryl cyanides (or aryl methanol and adjacent halogen aryl cyanides), ruthenium catalyst, palladium salt, azacyclo- imidazoles
The molar ratio of salt and alkali is 1: 1~2: 0.02~0.1: 0.03~0.1: 0.05~0.15: 0.1~0.3: 2~6.
The preparation method of the condensed biaryl azatropylidene -5- ketone compounds, further preferred technical solution are：
The reaction temperature is 100-160 DEG C, reaction time 6-24h, is purified after reaction to product with recrystallization.
The method of the present invention is led to using the available ruthenium of commodity, palladium metal catalyst, co-catalysis aryl methanol and aryl cyanides
It crosses hydrogen transfer reaction and carbon-hydrogen bond activation reacts a step and generates condensed biaryl azatropylidene -5- ketone compounds, have for synthesis
The substituted fused biaryl azatropylidene -5- ketones derivants of pharmaceutical activity provide an economical and practical preparation method.The party
Method is easy to operate, and the cheap range of reaction substrate is wide, environmental pollution is small, and economical in reaction is efficient, has important application value.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described：
Embodiment 1：Condensed biaryl azatropylidene -5- ketone compounds, general formula are (II), and concrete structure can be：
Here is the preparation method experimental example that preceding sections condense biaryl azatropylidene -5- ketone compounds.
Embodiment 2 condenses the preparation of biaryl azatropylidene -5- ketone compounds (1)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol benzyl alcohols, 2.0mmol benzonitriles, 0.02mmol RuH2(PPh3)4, 0.03mmol palladiums, 0.05mmol 1,
Bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of 3-, 0.1mmol silver oxides, 3.0mmol sodium hydrides and 5ml toluene, are set with nitrogen
Change reaction tube 3 times, then under magnetic stirring with oil bath heating to 110 DEG C, reaction reflux 20 hours.Remove oil bath, drops to room
Temperature；To reaction solution plus 3ml water, three times with the dichloromethane extraction of 5ml, merge organic phase and with anhydrous MgSO4It is 30 minutes dry,
Filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is recrystallized to give net product 1, yield using dichloromethane as solvent
82%.The nmr analysis data of the product are as follows：1H NMR. (400MHz, CDCl3)：δ 8.01 (d, 1H), 7.69-7.56 (m,
3H), 7.53-7.48 (m, 1H), 7.45 (td, 1H), 7.37 (td, 1H), 7.29 (dd, 1H), 6.66 (brs, 1H), 4.25 (dd,
1H), 3.96 (dd, 1H).
Embodiment 3 condenses the preparation of biaryl azatropylidene -5- ketone compounds (3)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol benzyl alcohols, 1.2mmol 3- chlorobenzonitriles, 0.1mmol RuH2(CO)(PPh3)3, 0.1mmol palladium bichlorides,
Bis- (2,6- diisopropylbenzyl) -4, the 5- glyoxalidine tetrafluoroborates of 0.15mmol 1,3-, 0.2mmol silver oxides, 3.0mmol
Sodium tert-butoxide and 5ml benzene are replaced reaction tube 3 times with nitrogen, then under magnetic stirring with oil bath heating to 100 DEG C, are reacted back
Stream 6 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, is extracted three times with the dichloromethane of 5ml, merge organic phase
Anhydrous MgSO is used in combination4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is molten with dichloromethane
Agent is recrystallized to give net product 2, yield 80%.The nmr analysis data of the product are as follows：1H NMR. (400MHz, CDCl3)：
8.01 (d, 1H), 7.63-7.49 (m, 4H), 7.43 (dd, 1H), 7.30 (d, 1H), 6.78 (brs, 1H), 4.21 (dd, 1H),
3.92 (dd, 1H).
Embodiment 4 condenses the preparation of biaryl azatropylidene -5- ketone compounds (6)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol benzyl alcohols, 1.1mmol 4- carbomethoxies benzonitrile, 0.05mmol RuH2(CO)(PPh3)3, 0.06mmol acetic acid
Palladium, 0.1mmol 1, bis- (2, the 6- diisopropyl phenyl) limidazoliums of 3-, 0.3mmol silver oxides, 6.0mmol potassium tert-butoxides and
5ml dioxane replaces reaction tube 3 times with nitrogen, then under magnetic stirring with oil bath heating to 110 DEG C, reaction reflux 10
Hour.Remove oil bath, drops to room temperature；It to reaction solution plus 3ml water, is extracted three times with the dichloromethane of 5ml, merges organic phase and be used in combination
Anhydrous MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is using dichloromethane as solvent, weight
Crystallization obtains net product 6, yield 80%.The nmr analysis data of the product are as follows：1H NMR. (400MHz, CDCl3)：δ8.28
(s, 1H), 8.06-8.02 (m, 2H), 7.64 (d, 2H), 7.58-7.52 (m, 1H), 7.38 (d, 1H), 7.01 (brs, 1H),
4.26 (dd, 1H), 4.03 (dd, 1H), 3.95 (s, 3H).
Embodiment 5 condenses the preparation of biaryl azatropylidene -5- ketone compounds (8)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol3 benzyl alcohols, 1.6mmol p-Fluorophenyl cyanides, 0.1mmol RuH2(CO)(PPh3)3, 0.09mmol palladiums,
Bis- (2,6- diisopropylbenzyl) -4, the 5- glyoxalidine tetrafluoroborates of 0.13mmol 1,3-, 0.1mmol silver oxides, 5.0mmol
Sodium hydride and 5ml dimethyl sulfoxide (DMSO)s replace reaction tube 3 times with nitrogen, then under magnetic stirring with oil bath heating to 160 DEG C,
Reaction reflux 18 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, is extracted three times, merged with the dichloromethane of 5ml
Organic phase and with anhydrous MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is with dichloromethane
Alkane is solvent, is recrystallized to give net product 8, yield 85%.The nmr analysis data of the product are as follows：1H NMR. (400MHz,
CDCl3)：8.00 (d, 1H), 7.63-7.48 (m, 4H), 7.15 (td, 1H), 7.02 (dd, 1H), 6.85 (brs, 1H), 4.22
(dd, 1H), 3.99 (dd, 1H).
Embodiment 6 condenses the preparation of biaryl azatropylidene -5- ketone compounds (11)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol bromophenyls methanol, 1.3mmol 3- trifluoromethylbenzonitriles, 0.1mmol RuH2(PPh3)4, 0.1mmol acetic acid
Palladium, 0.15mmol 1, bis- (2,6- diisopropylbenzyl) -4, the 5- glyoxalidine tetrafluoroborates of 3-, 0.15mmol silver oxides,
4.0mmol sodium hydrides and 5ml n,N-Dimethylformamide replace reaction tube 3 times with nitrogen, then use oil under magnetic stirring
Bath is heated to 160 DEG C, reaction reflux 20 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, with the dichloromethane of 5ml
Alkane extracts three times, merges organic phase and with anhydrous MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, after concentration
Solid using dichloromethane as solvent, be recrystallized to give net product 11, yield 80%.The nmr analysis data of the product are as follows：1H NMR. (400MHz, CDCl3)：8.00 (d, 1H), 7.60-7.48 (m, 4H), 7.41 (dd, 1H), 7.26 (d, 1H), 6.76
(brs, 1H), 4.20 (dd, 1H), 3.90 (dd, 1H).
Embodiment 7 condenses the preparation of biaryl azatropylidene -5- ketone compounds (13)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol to bromobenzene methanol, 1.3mmol 3- methyl benzonitriles, 0.08mmol RuH2(CO)(PPh3)3, 0.1mmol chlorinations
Palladium, 0.15mmol 0.1mmol 1, bis- (2, the 6- diisopropyl phenyl) limidazoliums of 3-, 0.2mmol silver oxides, uncle 3.0mmol
Sodium butoxide and 5ml toluene are replaced reaction tube 3 times with nitrogen, then under magnetic stirring with oil bath heating to 110 DEG C, are reacted back
Stream 24 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, is extracted three times with the dichloromethane of 5ml, merge organic phase
Anhydrous MgSO is used in combination4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is molten with dichloromethane
Agent is recrystallized to give net product 13, yield 85%.The nmr analysis data of the product are as follows：1H NMR. (400MHz, CDCl3)：
8.02 (d, 1H), 7.86 (d, 1H), 7.65 (d, 1H), 7.35 (d, 1H), 7.12 (d, 1H), 7.03 (d, 1H), 6.73 (brs,
1H), 4.18 (dd, 1H), 3.87 (dd, 1H), 2.37 (s, 3H).
Embodiment 8 condenses the preparation of biaryl azatropylidene -5- ketone compounds (15)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol 3- methylbenzyl alcohols, 1.3mmol p-Fluorophenyl cyanides, 0.06mmol RuH2(CO)(PPh3)3, 0.08mmol acetic acid
Palladium, 0.15mmol 1, bis- (2,6- diisopropylbenzyl) -4, the 5- glyoxalidine tetrafluoroborates of 3-, 0.1mmol silver oxides,
3.0mmol sodium hydrides and 5ml dioxane, with nitrogen displacement reaction tube 3 times, then under magnetic stirring with oil bath heating extremely
110 DEG C, reaction reflux 24 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, three are extracted with the dichloromethane of 5ml
It is secondary, merge organic phase and with anhydrous MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, the solid after concentration with
Dichloromethane is solvent, is recrystallized to give net product 15, yield 76%.The nmr analysis data of the product are as follows：1H NMR.
(400MHz, CDCl3)：(8.01 d, 1H), 7.88 (d, 1H), 7.67 (d, 1H), 7.42 (d, 1H), 7.20 (d, 1H), 7.12 (d,
1H), 6.87 (brs, 1H), 4.25 (dd, 1H), 4.00 (dd, 1H), 2.36 (s, 3H).
Embodiment 9 condenses the preparation of biaryl azatropylidene -5- ketone compounds (17)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol meta-methoxies benzyl alcohol, 1.5mmol 3- methoxy benzonitriles, 0.06mmol RuH2(PPh3)4, 0.1mmol vinegar
Sour palladium, 0.15mmol 1, bis- (2,6- diisopropylbenzyl) -4, the 5- glyoxalidine tetrafluoroborates of 3-, 0.3mmol silver oxides,
5.0mmol potassium tert-butoxides and 5ml dioxane replace reaction tube 3 times with nitrogen, then use oil bath heating under magnetic stirring
To 110 DEG C, reaction reflux 20 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, extracted with the dichloromethane of 5ml
Three times, merge organic phase and with anhydrous MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, the solid after concentration
Using dichloromethane as solvent, it is recrystallized to give net product 17, yield 88%.The nmr analysis data of the product are as follows：1H NMR.
(400MHz, CDCl3)：7.98 (d, 1H), 7.67 (d, 1H), 7.61 (d, 1H), 7.10 (dt, 1H), 7.02 (d, 1H), 6.78
(dd, 1H), 6.71 (brs, 1H), 4.15 (dd, 1H), 3.82 (dd, 1H), 3,80 (s, 3H), 3,77 (s, 3H).
Embodiment 10 condenses the preparation of biaryl azatropylidene -5- ketone compounds (21)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol to fluorophenyl methanol, 1.1mmol benzonitriles, 0.1mmol RuH2(CO)(PPh3)3, 0.06mmol palladium bichlorides,
Bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of 0.12mmol 1,3-, 0.1mmol silver oxides, 6.0mmol sodium tert-butoxides and 5ml
Toluene replaces reaction tube 3 times with nitrogen, then under magnetic stirring with oil bath heating to 110 DEG C, reaction reflux 22 hours.It goes
Fall oil bath, drops to room temperature；To reaction solution plus 3ml water, three times with the dichloromethane extraction of 5ml, merge organic phase and with anhydrous
MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is using dichloromethane as solvent, recrystallization
Obtain net product 21, yield 83%.The nmr analysis data of the product are as follows：1H NMR. (400MHz, CDCl3)：8.01 (d,
1H), 7.64-7.50 (m, 4H), 7.17 (td, 1H), 7.03 (dd, 1H), 6.87 (brs, 1H), 4.25 (dd, 1H), 4.00 (dd,
1H)。
Embodiment 11 condenses the preparation of biaryl azatropylidene -5- ketone compounds (25)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol 4- methylbenzyl alcohols, 1.5mmol to trifluoromethylbenzonitrile, 0.1mmol RuH2(PPh3)4, 0.1mmol acetic acid
Palladium, 0.15mmol 1, bis- (2,6- diisopropylbenzyl) -4, the 5- glyoxalidine tetrafluoroborates of 3-, 0.2mmol silver oxides,
5.0mmol sodium hydrides and 5ml toluene replace reaction tube 3 times, then under magnetic stirring with oil bath heating to 110 with nitrogen
DEG C, reaction reflux 18 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, extracted three times with the dichloromethane of 5ml,
Merge organic phase and with anhydrous MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is with two
Chloromethanes is solvent, is recrystallized to give net product 25, yield 83%.The nmr analysis data of the product are as follows：1H NMR.
(400MHz, CDCl3)：8.03 (d, 1H), 7.73 (d, 1H), 7.69 (d, 1H), 7.52 (d, 1H), 7.44 (d, 1H), 7.28
(dd, 1H), 6.96 (brs, 1H), 4.42 (dd, 1H), 4.26 (dd, 1H), 2.37 (s, 3H).
Embodiment 12 condenses the preparation of biaryl azatropylidene -5- ketone compounds (27)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter fluorobenzonitrile, 0.05mmol RuH between 1.0mmol 3- methylbenzyl alcohols, 1.3mmol2(CO)(PPh3)3, 0.1mmol chlorinations
Palladium, 0.12mmol 1, bis- (2, the 6- diisopropyl phenyl) limidazoliums of 3-, 0.2mmol silver oxides, 5.0mmol sodium tert-butoxides and
5ml benzene replaces reaction tube 3 times with nitrogen, then under magnetic stirring with oil bath heating to 100 DEG C, reaction reflux 16 hours.It goes
Fall oil bath, drops to room temperature；To reaction solution plus 3ml water, three times with the dichloromethane extraction of 5ml, merge organic phase and with anhydrous
MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is using dichloromethane as solvent, recrystallization
Obtain net product 27, yield 79%.The nmr analysis data of the product are as follows：1H NMR. (400MHz, CDCl3)：8.00 (d,
1H), 7.70 (d, 1H), 7.67 (d, 1H), 7.50 (d, 1H), 7.42 (d, 1H), 7.24 (dd, 1H), 6.92 (brs, 1H), 4.40
(dd, 1H), 4.25 (dd, 1H), 2.35 (s, 3H).
Embodiment 13 condenses the preparation of biaryl azatropylidene -5- ketone compounds (30)：
Under nitrogen protection, add to the Schlek reaction tubes of 10ml (commonly a kind of glass apparatus when anhydrous and oxygen-free operates)
Enter 1.0mmol to methylbenzyl alcohol, 1.2mmol 4- methoxy benzonitriles, 0.08mmol RuH2(CO)(PPh3)3、0.1mmol
Palladium, 0.12mmol 1, bis- (2,6- diisopropylbenzyl) -4, the 5- glyoxalidine tetrafluoroborates of 3-, 0.1mmol silver oxides,
3.0mmol sodium hydrides and 5ml toluene replace reaction tube 3 times, then under magnetic stirring with oil bath heating to 110 with nitrogen
DEG C, reaction reflux 18 hours.Remove oil bath, drops to room temperature；To reaction solution plus 3ml water, extracted three times with the dichloromethane of 5ml,
Merge organic phase and with anhydrous MgSO4It is 30 minutes dry, filtering；Filtrate is concentrated with rotary evaporator, and the solid after concentration is with two
Chloromethanes is solvent, is recrystallized to give net product 30, yield 89%.The nmr analysis data of the product are as follows：1H NMR.
(400MHz, CDCl3)：8.00 (d, 1H), 7.71 (d, 1H), 7.67 (d, 1H), 7.50 (d, 1H), 7.41 (d, 1H), 7.25
(dd, 1H), 6.92 (brs, 1H), 4.17 (dd, 1H), 3.84 (dd, 1H), 3,76 (s, 3H), 2.35 (s, 3H).
Claims (9)
1. a kind of condensed biaryl azatropylidene -5- ketone compounds, which is characterized in that the condensed biaryl azatropylidene -5-
The structural formula of ketone compounds is such as shown in (II)：
R1、R2Selected from-H ,-CH3、-CF3、-OCH3、-C2H5、-OC2H5、-C6H5、-CH2C6H5、-NO2、-COCH3、-COOCH3、-
CHO、-F、-Cl、-Br；R1In aromatic ring 1-4, R2Any position on aromatic ring 8-11.
2. a kind of preparation method of condensed biaryl azatropylidene -5- ketone compounds as described in claim 1, step is such as
Under：Aryl methanol and aryl cyanides, ruthenium catalyst, palladium salt, azacyclo- imidazole salts, silver oxide and alkali is taken to be added to organic solvent
In, in N2It is heated under gas shielded, processing after reaction obtains the condensed biaryl azatropylidene -5- ketone compounds；
The structural formula of the aryl methanol and aryl cyanides is such as shown in (I)：
The R of the aryl methanol, aryl cyanides1、R2Group and the R in condensed biaryl azatropylidene -5- ketone compounds1、R2Base
Group's connotation is identical：R1、R2Selected from-H ,-CH3、-CF3、-OCH3、-C2H5、-OC2H5、-C6H5、-CH2C6H5、-NO2、-COCH3、-
COOCH3、-CHO、-F、-Cl、-Br；R1In aromatic ring 1-4, R2Any position on aromatic ring 8-11.
3. the preparation method of condensed biaryl azatropylidene -5- ketone compounds as claimed in claim 2, it is characterised in that：It is described
Ruthenium catalyst be selected from RuH2(PPh3)4、RuH2(CO)(PPh3)3。
4. the preparation method of condensed biaryl azatropylidene -5- ketone compounds as claimed in claim 2, it is characterised in that：It is described
Palladium salt be selected from palladium bichloride or palladium.
5. the preparation method of condensed biaryl azatropylidene -5- ketone compounds as claimed in claim 2, it is characterised in that：It is described
Azacyclo- imidazole salts be selected from bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of 1,3-, 1,3- bis- (2,6- diisopropyl phenyl) bromines
Change imidazoles, 1,3- bis- (2,6- diisopropylbenzyl) -4,5- glyoxalidine tetrafluoroborates.
6. condensed biaryl and the preparation method of azatropylidene -5- ketone compounds as claimed in claim 2, it is characterised in that：Institute
The organic solvent stated is selected from benzene, toluene, dioxane, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO).
7. condensed biaryl and the preparation method of azatropylidene -5- ketone compounds as claimed in claim 2, it is characterised in that：Institute
The molar ratio for stating adjacent halogen aryl methanol and aryl cyanides, ruthenium catalyst, palladium salt, azacyclo- imidazole salts, silver oxide and alkali is 1: 1~
2: 0.02~0.1: 0.03~0.1: 0.05~0.15: 0.1~0.3: 2~6.
8. condensed biaryl and the preparation method of azatropylidene -5- ketone compounds as claimed in claim 2, it is characterised in that：Institute
It is 100-160 DEG C, reaction time 6-24h to state reaction temperature, is purified after reaction to product with recrystallization.
9. the preparation method of condensed biaryl azatropylidene -5- ketone compounds as claimed in claim 2, it is characterised in that：It is described
Alkali be selected from sodium hydride, sodium tert-butoxide, potassium tert-butoxide.
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