CN107382895A - A kind of synthetic method of 2 Ben bases Benzooxazole kind compound - Google Patents
A kind of synthetic method of 2 Ben bases Benzooxazole kind compound Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D263/57—Aryl or substituted aryl radicals
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Abstract
The invention provides a kind of synthetic method of 2 Ben bases Benzooxazole kind compound, directly reacted using nano oxidized copper catalysis benzoxazole and end-group alkyne and prepare 2 benzene base Benzooxazole kind compounds, synthetic method is simple, raw material is easy to get, cost is low, operates more convenient, efficiency high, it is adapted to a variety of reaction substrates, and catalyst being capable of recycling.Compared with prior art, the nanometer copper oxide catalyst that the present invention uses simply easily is made, and stable performance, catalytic effect is good and can recycle；Raw material benzoxazole and terminal alkyne are reacted, and reaction condition is gentle, it is not necessary to use noble metal or strong contaminative metal reagent；This reaction system cost is cheap, simple efficient, environment-friendly, can synthesize 2 Ben base Benzooxazole kind compounds of high yield, be advantageous to industrial production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthesis side of 2- Ben bases Benzooxazole kind compound
Method, 2- benzene base Benzooxazole kind compounds are prepared using nanometer copper catalysis.
Background technology
In organic chemistry research, heterocycle compound is an important component of organic chemistry filed, Er Qieqi
Quite varied application has been obtained in organic synthesis.Moreover, heterocycle compound is passed through frequently as some pharmaceutical synthesis
Intermediate.Some compounds of heterocycle have been confirmed to be good pharmaceutical activity at present, and the application in medicine is very universal,
It is increasingly becoming the main source of medicine.Scientist also is directed to working out multiple heterocycles probing into the reaction of heterocycle and alkynes in recent years
Research for medicine, biochemistry etc..It is part heterocyclic drug structural formula below：
Mainly there is following several the synthetic method of report 2- Ben base Benzooxazole kind compounds in document：
(1) 2010 year Toshiaki Murai seminar holds the mixing of axle 1,10- Phens cationic palladium using one and urged
Agent is catalyzed heterocycle and iodobenzene synthesis 2- Ben base Benzooxazole kind compounds.
The method used catalyst is not only expensive but also complicated.
(2) 2013 years Jiang Cheng seminars utilize palladium catalyst catalysis benzoxazole and acetylenic acid reaction generation 2- benzene
Base Benzooxazole kind compound.
Though the method yield is very high, reaction uses palladium expensive catalyst and mixed solvent.
(3) 2014 years Dipannita Kalyani seminars catalyze and synthesize 2- Ben base Benzooxazole kinds using palladium catalyst
Compound.
Zhong-Xia Wang seminars utilize palladium metal compound for catalysis benzoxazole and thioether reactant within (four) 2015 years
Synthesize 2- Ben base Benzooxazole kind materials.
(5) 2016 years Sunwoo Lee seminars utilize palladium chtalyst, PAR-2Hg2+Chemistry of the compound as halide ion
Sensor is so as to synthesizing 2- Ben base Benzooxazole kind compounds.
The method utilizes PAR-2Hg2+Compound can be realized as the chemical sensor of aryl iodide, aryl bromide, aryl chloride
Suzuki coupling reactions.But this Chemical sensors contaminative is too big.
In summary, prior art synthesis 2- Ben base Benzooxazole kind compound methods are although more, but these method bases
Complicated part will be used in sheet；Although some substrate applicabilities are wide, required reactant prepares cumbersome, there is one in operation
Fixed difficulty；Some reaction time are long, and reaction yield is relatively low；The compound contaminative that some are used is very strong, is not suitable for
A large amount of industrial productions.More importantly this kind of reaction is catalyst mostly using the noble metal such as palladium, reaction cost costly and
And it is not recyclable, it is not suitable for industrial production.
Therefore it provides a kind of novel method for synthesizing of 2- Ben bases Benzooxazole kind compound is necessary.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of 2- Ben bases Benzooxazole kind compound, utilization are nano oxidized
Copper catalysis benzoxazole and end-group alkyne, which directly react, prepares 2- Ben base Benzooxazole kind compounds, and synthetic method is simple, and raw material is easy
, cost is low, operates more convenient, efficiency high, is adapted to a variety of reaction substrates, and catalyst being capable of recycling.
Present invention also offers a kind of 2- Ben bases Benzooxazole kind compound, obtained using the above method.
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound provided by the invention, comprises the following steps：
A, after mixing catalyst, benzoxazole, terminal alkyne, oxide and alkali, solvent is added, in oxygen atmosphere,
Heating stirring back flow reaction；
B, after reaction terminates, product, by column chromatographic isolation and purification, obtains 2- phenyl benzos after extracting, dry, concentrate
Oxazole compounds.
Benzoxazole, terminal alkyne, catalyst, oxide, alkali mol ratio are 1 in step A：1.2-1.5：0.15-0.2：
1：2.
The concentration of benzoxazole in a solvent is 0.1mmol/mL in step A.
Relative to 0.2mmol the benzoxazole, -0.3mmol of terminal alkyne dosage 0.24, the oxide dosage
0.2mmol, the base amount 0.4mmol, the solvent load 2mL；Catalyst amount is the 15%- of benzoxazole dosage
20%.
Terminal alkyne structural formula described in step A is：
Wherein R1Selected from 4-H, 4-CH3、3-CH3、2-CH3、4-OCH3、3-OCH3、2-OCH3、4-Cl、3-Cl、2-Cl、4-F、4-C
(CH3)3、4-OCH2CH3Or 4- (CH2)4CH3In any one.
Benzoxazole structural formula described in step A is：
Wherein R2Selected from 5-H, 5-CH3, 5-Cl or 6-CH3In any one.
Catalyst described in step A is fusiformis nano cupric oxide, flake nano cupric oxide, appointing in particle nano cupric oxide
Meaning is a kind of, can reclaim and recycle.The catalyst of different-shape all can preferably promote the synthesis of product in this reaction,
Wherein flake nano catalyst effect is especially pronounced.
The specific preparation method of various catalyst is as follows in step A：
Take 40mL distilled water to be added in 100mL beakers, weigh 0.3194g Cu (CH3COO)2·H2O solids are placed in
In beaker, its dissolving is made in the case of 30 DEG C of magnetic agitations, then is slowly dropped into 1M NH3·H2O solution adjusts pH value, will burn
Cup preservative film parcel is put in baking oven, and 24h is reacted under the conditions of 65 DEG C and is cooled to room temperature, then respectively with distilled water and anhydrous
Ethanol respectively twice of cleaning, separation centrifuge, and vacuum drying 5h can be prepared by the nano cupric oxide of different-shape under the conditions of 60 DEG C.This is anti-
PH 7 obtains fusiformis nano cupric oxide in answering；PH 8.5, flake nano cupric oxide.
The preparation method of particle nanometer CuO in step A：Take 0.4525g Cu (CH3COO)2It is dissolved in 50mL absolute ethyl alcohols,
It is placed in after its dissolving in capacity 60mL polytetrafluoroethylene (PTFE) autoclave and reacts 20h under the conditions of 150 DEG C, is cooled to room temperature, then
2 times and washes of absolute alcohol 3 times are cleaned with distilled water, separation centrifugation, be dried in vacuo to obtain black powder under room temperature condition respectively.
Heating stirring back flow reaction is specially described in step A：Reaction 9- is stirred at reflux under conditions of 140-150 DEG C
11h。
Alkali described in step A is any one in sodium hydroxide, potassium hydroxide, potassium carbonate or cesium carbonate.
Solvent described in step A is any one or two in N,N-dimethylformamide DMF or dimethyl sulfoxide (DMSO) DMSO
Kind.
It is any one in silver oxide, silver carbonate, silver nitrate or silver acetate described in oxide in step A.
Step B is specially：Products therefrom petroleum ether and saturated aqueous common salt are extracted, anhydrous magnesium sulfate is dried, and decompression is dense
Contracting, obtains crude product, using petrol ether/ethyl acetate as solvent, 2- Ben base Benzooxazole kind chemical combination is obtained by column chromatography for separation
Thing.
Wherein, the volume ratio of petroleum ether and ethyl acetate is 100:1.
A kind of 2- Ben bases Benzooxazole kind compound provided by the invention, synthesizes to obtain using the above method.
Preferably, the synthetic method of the 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, by 0.03mmol flake nanos cupric oxide, 0.2mmol benzoxazoles, 0.3mmol terminal alkynes, 0.2mmol oxygen
Change silver, 0.4mmol cesium carbonates, add dimethyl sulfoxide (DMSO) (DMSO) 2mL, be stirred at reflux under conditions of oxygen atmosphere, 150 DEG C anti-
Answer 11h；
B, product obtains 2- Ben base Benzooxazole kinds by petroleum ether column chromatographic isolation and purification after extracting, dry, concentrate
Compound.
Mechanism of the present invention is as follows：First under Ag (I) assistance, phenylacetylene and nano cupric oxide form phenylacetylene base oxidation
Copper, due to the effect of oxygen, two molecule alkynes carbon are oxidized to diketone so as to form intermediate product, and then the CO of two equivalents is extracted
It is middle and then because phenyl cupric oxide electrophilic attack benzoxazole is so as to form intermediate so as to form phenyl cupric oxide
Product restores elimination and forms arylated products and nano cupric oxide.We also did nano cupric oxide recovery experiment, experiment knot
Fruit shows multiple recovery experiment, and yield is still very high.
Compared with prior art, the nanometer copper oxide catalyst that the present invention uses simply easily is made, stable performance, catalytic effect
Well and it can recycle；Raw material benzoxazole and terminal alkyne are reacted, and reaction condition is gentle, it is not necessary to use noble metal
Or strong contaminative metal reagent；This reaction system cost is cheap, simple efficient, environment-friendly, can synthesize the 2- benzene of high yield
Base Benzooxazole kind compound, is advantageous to industrial production.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 1；
Fig. 2 is the carbon-13 nmr spectra figure of embodiment 1；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 2；
Fig. 4 is the carbon-13 nmr spectra figure of embodiment 2；
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 3；
Fig. 6 is the carbon-13 nmr spectra figure of embodiment 3；
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 4；
Fig. 8 is the carbon-13 nmr spectra figure of embodiment 4；
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 5；
Figure 10 is the carbon-13 nmr spectra figure of embodiment 5；
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 6；
Figure 12 is the carbon-13 nmr spectra figure of embodiment 6；
Figure 13 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 7；
Figure 14 is the carbon-13 nmr spectra figure of embodiment 7；
Figure 15 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 8；
Figure 16 is the carbon-13 nmr spectra figure of embodiment 8；
Figure 17 is reaction equation.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, it is not limited to these embodiments.In embodiment, the alkynes of different substituents,
Benzoxazole, silver oxide, silver carbonate, silver acetate, potassium hydroxide, sodium hydroxide, cesium carbonate, DMF, DMSO are Chinese medicines group chemistry
Reagent Co., Ltd product.
Embodiment 1
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, weigh respectively 0.03mmol flake nanos cupric oxide, 0.2mmol benzoxazoles, 0.3mmol phenylacetylenes,
0.2mmol silver oxides, 0.4mmol cesium carbonates, dimethyl sulfoxide (DMSO) (DMSO) 2mL is added, under conditions of oxygen atmosphere, 150 DEG C
It is stirred at reflux reaction 9h；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (volume ratio 100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation to purify
White solid is 2- Ben base benzoxazoles, yield 90%, 103-104 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3)δ8.22-8.20(m,2H),7.74-7.72(m,1H),7.54-7.47(m,4H),
7.32-7.29(m,2H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ163.0,150.8,142.1,131.5,128.9,127.2,125.1,124.6,
120.0,110.6.
Embodiment 2
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, 0.03mmol fusiformis nano cupric oxide, 0.2mmol 5- Jia bases benzoxazole, 0.3mmol3- chlorobenzenes are weighed respectively
Acetylene, 0.2mmol silver oxides, 0.4mmol cesium carbonates, dimethyl sulfoxide (DMSO) (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of bar
Reaction 11h is stirred at reflux under part；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (volume ratio 100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation to purify
White solid is 2- (3- chlorphenyls) -5- Jia base benzoxazoles, yield 70%, 105-106 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3) δ 8.18 (s, 1H), 8.06 (d, J=7.8Hz, 1H), 7.50 (s, 1H), 7.42-
7.36 (m, 3H), 7.12 (d, J=8.1Hz, 1H), 2.43 (s, 3H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ161.7,149.0,142.1,135.0,134.7,131.3,130.2,129.0,
127.5,126.7,125.6,120.1,110.0,21.5.
Embodiment 3
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, 0.03mmol particles nano cupric oxide, 0.2mmol benzoxazoles, 0.3mmol 4- ethoxybenzene second are weighed respectively
Alkynes, 0.2mmol silver oxides, 0.4mmol cesium carbonates, dimethyl sulfoxide (DMSO) (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition
Under be stirred at reflux reaction 11h；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation and purify white solid
Body is 2- (4- ethoxyl phenenyl) benzoxazoles, yield 78%, 91-92 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3) δ 8.13 (d, J=8.4Hz, 2H), 7.69-7.67 (m, 1H), 7.51-7.48 (m,
1H), 7.28-7.20 (m, 2H), 7.00-6.94 (m, 2H), 4.06 (q, J=7.2Hz, 2H), 1.40 (t, J=7.2Hz, 3H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ161.8,150.7,142.3,129.4,124.5,124.4,119.6,119.5,
114.8,110.4,63.7,14.7.
Embodiment 4
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, weigh respectively 0.03mmol flake nanos cupric oxide, 0.2mmol benzoxazoles, 0.3mmol phenylacetylenes,
0.2mmol silver oxides, 0.4mmol potassium hydroxide, dimethyl sulfoxide (DMSO) (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition
Under be stirred at reflux reaction 11h；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation and purify white solid
Body is 2- Ben base benzoxazoles, yield 40%, 103-104 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3)δ8.22-8.20(m,2H),7.74-7.72(m,1H),7.54-7.47(m,4H),
7.32-7.29(m,2H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ163.0,150.8,142.1,131.5,128.9,127.2,125.1,124.6,
120.0,110.6.
Embodiment 5
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, 0.03mmol flake nanos cupric oxide, 0.2mmol benzoxazoles, 0.3mmol 4- methylbenzene second are weighed respectively
Alkynes, 0.2mmol silver carbonates, 0.4mmol cesium carbonates, dimethyl sulfoxide (DMSO) (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition
Under be stirred at reflux reaction 11h；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (volume ratio 100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation to purify
White solid is 2- (4- aminomethyl phenyl) benzoxazoles, yield 89%, 115-116 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3) δ 8.10 (d, J=8.1Hz, 2H), 7.73-7.70 (m, 1H), 7.53-7.50 (m,
1H),7.29-7.27(m,4H),2.39(s,3H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ163.3,150.7,142.2,142.1,129.6,127.6,124.9,124.5,
119.8,110.5,21.7.
Embodiment 6
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, 0.03mmol flake nanos cupric oxide, 0.2mmol benzoxazoles, 0.3mmol 4- tert-butyl benzene second are weighed respectively
Alkynes, 0.2mmol silver acetates, 0.4mmol cesium carbonates, dimethyl sulfoxide (DMSO) (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition
Under be stirred at reflux reaction 11h；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (volume ratio 100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation to purify
White solid is 2- (4- tert-butyl-phenyl) benzoxazoles, yield 70%, 99-100 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3) δ 8.13 (d, J=8.1Hz, 2H), 7.73-7.70 (m, 1H), 7.52-7.48 (m,
3H),7.30-7.28(m,2H),1.32(s,9H).
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ163.2,155.1,150.7,142.2,127.5,125.9,124.9,124.5,
119.9,110.5,31.2.
Embodiment 7
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, 0.03mmol flake nanos cupric oxide, 0.2mmol benzoxazoles, 0.3mmol 2- methoxybenzene second are weighed respectively
Alkynes, 0.2mmol silver oxides, 0.4mmol sodium hydroxides, dimethyl sulfoxide (DMSO) (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of bar
Reaction 11h is stirred at reflux under part；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation and purify white solid
Body is 2- (2- methoxyphenyl) benzoxazoles, yield 71%, 46-47 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3) δ 8.09 (d, J=7.2Hz, 1H), 7.78 (b, 1H), 7.54-7.44 (m, 2H),
7.30-7.29(m,2H),7.08-7.03(m,2H)；3.98(s,3H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ161.6,158.5,150.3,142.1,132.8,131.3,124.9,124.3,
120.7,120.2,112.1,110.4,56.2.
Embodiment 8
A kind of synthetic method of 2- Ben bases Benzooxazole kind compound, comprises the following steps：
A, 0.03mmol flake nanos cupric oxide, 0.2mmol benzoxazoles, 0.3mmol 4-n amylbenzene second are weighed respectively
Alkynes, 0.2mmol silver oxides, 0.4mmol cesium carbonates, add DMF (DMF) 2mL, in oxygen atmosphere, 150 DEG C
Under conditions of be stirred at reflux reaction 11h；
B, room temperature is cooled to after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated aqueous common salt, and by gained organic phase
Dried, concentrated, with petrol ether/ethyl acetate (100 with anhydrous magnesium sulfate:1) make solvent column chromatography for separation and purify white solid
Body is 2- (4-n amyl groups phenyl) benzoxazole, yield 71%, 43-44 DEG C of fusing point.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3) δ 8.11 (d, J=8.1Hz, 2H), 7.73-7.70 (m, 1H), 7.54-7.51 (m,
1H), 7.30-7.27 (m, 4H), 2.63 (t, J=7.5Hz, 2H), 1.61 (t, J=6.6Hz, 2H), 1.31-1.29 (m, 4H),
0.85 (t, J=6.5Hz, 3H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3)δ165.4,150.7,147.1,142.2,129.0,127.6,124.9,124.5,
119.8,110.5,36.0,31.5,30.9,22.5,14.0。
Claims (9)
1. a kind of synthetic method of 2- Ben bases Benzooxazole kind compound, it is characterised in that the synthetic method includes following step
Suddenly：
A, after mixing catalyst, benzoxazole, terminal alkyne, oxide and alkali, solvent is added, in oxygen atmosphere, heating
It is stirred at reflux reaction；
B, after reaction terminates, product, by column chromatographic isolation and purification, obtains 2- Ben base benzoxazoles after extracting, dry, concentrate
Class compound.
2. the synthetic method of 2- Ben bases Benzooxazole kind compound according to claim 1, it is characterised in that in step A
Benzoxazole, terminal alkyne, catalyst, oxide, alkali mol ratio are 1：1.2-1.5：0.15-0.2：1：2.
3. the synthetic method of 2- Ben bases Benzooxazole kind compound according to claim 1 or 2, it is characterised in that step A
Described in terminal alkyne structural formula be：
Wherein R1Selected from 4-H, 4-CH3、3-CH3、2-CH3、4-OCH3、3-OCH3、2-OCH3、4-Cl、3-Cl、2-Cl、4-F、4-C
(CH3)3、4-OCH2CH3Or 4- (CH2)4CH3In any one.
4. the synthetic method of the 2- Ben base Benzooxazole kind compounds according to claim any one of 1-3, it is characterised in that
Benzoxazole structural formula described in step A is：
Wherein R2Selected from 5-H, 5-CH3, 5-Cl or 6-CH3In any one.
5. the synthetic method of the 2- Ben base Benzooxazole kind compounds according to claim any one of 1-4, it is characterised in that
Heating stirring back flow reaction is specially described in step A：Reaction 9-11h is stirred at reflux under conditions of 140-150 DEG C.
6. the synthetic method of the 2- Ben base Benzooxazole kind compounds according to claim any one of 1-5, it is characterised in that
Alkali described in step A is any one in sodium hydroxide, potassium hydroxide, potassium carbonate or cesium carbonate.
7. the synthetic method of the 2- Ben base Benzooxazole kind compounds according to claim any one of 1-6, it is characterised in that
Solvent described in step A is any one or two kinds in N,N-dimethylformamide DMF or dimethyl sulfoxide (DMSO) DMSO.
8. the synthetic method of the 2- Ben base Benzooxazole kind compounds according to claim any one of 1-7, it is characterised in that
It is any one in silver oxide, silver carbonate, silver nitrate or silver acetate described in oxide in step A.
9. the synthetic method of the 2- Ben base Benzooxazole kind compounds according to claim any one of 1-8, it is characterised in that
Step B is specially：Products therefrom petroleum ether and saturated aqueous common salt are extracted, anhydrous magnesium sulfate is dried, and is concentrated under reduced pressure, is obtained and slightly produce
Thing, using petrol ether/ethyl acetate as solvent, 2- Ben base Benzooxazole kind compounds are obtained by column chromatography for separation.
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| CN114605341A (en) * | 2022-04-25 | 2022-06-10 | 安徽师范大学 | Benzisoxazole compound and preparation method thereof |
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| CN107382895B (en) | 2019-09-27 |
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