CN107382895B - A kind of synthetic method of 2- phenyl benzoxazoles class compound - Google Patents
A kind of synthetic method of 2- phenyl benzoxazoles class compound Download PDFInfo
- Publication number
- CN107382895B CN107382895B CN201710652421.6A CN201710652421A CN107382895B CN 107382895 B CN107382895 B CN 107382895B CN 201710652421 A CN201710652421 A CN 201710652421A CN 107382895 B CN107382895 B CN 107382895B
- Authority
- CN
- China
- Prior art keywords
- benzoxazoles
- class compound
- phenyl
- synthetic method
- reaction
- 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.)
- Active
Links
- -1 2- phenyl benzoxazoles class compound Chemical class 0.000 title claims abstract description 44
- 238000010189 synthetic method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000000183 1,3-benzoxazoles Chemical class 0.000 claims abstract description 27
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 23
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000005751 Copper oxide Substances 0.000 claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000047 product Substances 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 10
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 229910001923 silver oxide Inorganic materials 0.000 claims description 9
- FIISKTXZUZBTRC-UHFFFAOYSA-N 2-phenyl-1,3-benzoxazole Chemical class C1=CC=CC=C1C1=NC2=CC=CC=C2O1 FIISKTXZUZBTRC-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007445 Chromatographic isolation Methods 0.000 claims description 3
- 238000011097 chromatography purification Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- KWOXDLBKAWFYOJ-UHFFFAOYSA-N 2-(2-methoxyphenyl)-1,3-benzoxazole Chemical class COC1=CC=CC=C1C1=NC2=CC=CC=C2O1 KWOXDLBKAWFYOJ-UHFFFAOYSA-N 0.000 description 1
- IEAFYCBGSWUVQT-UHFFFAOYSA-N 2-(3-chlorophenyl)-5-methyl-1,3-benzoxazole Chemical compound N=1C2=CC(C)=CC=C2OC=1C1=CC=CC(Cl)=C1 IEAFYCBGSWUVQT-UHFFFAOYSA-N 0.000 description 1
- ZNBHIZVPIRZVLA-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-1,3-benzoxazole Chemical class C1=CC(C(C)(C)C)=CC=C1C1=NC2=CC=CC=C2O1 ZNBHIZVPIRZVLA-UHFFFAOYSA-N 0.000 description 1
- UBIAVBGIRDRQLD-UHFFFAOYSA-N 5-methyl-1,3-benzoxazole Chemical compound CC1=CC=C2OC=NC2=C1 UBIAVBGIRDRQLD-UHFFFAOYSA-N 0.000 description 1
- 206010001497 Agitation Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- XTFNBGUXOKGTDK-UHFFFAOYSA-N [4-(1,3-benzoxazol-2-yl)phenyl]methanamine Chemical class C1=CC(CN)=CC=C1C1=NC2=CC=CC=C2O1 XTFNBGUXOKGTDK-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- 150000001503 aryl iodides Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention provides a kind of synthetic methods of 2- phenyl benzoxazoles class compound, benzoxazoles and end-group alkyne, which are catalyzed, using nano cupric oxide directly reacts preparation 2- phenyl benzoxazoles class compound, synthetic method is simple, raw material is easy to get, at low cost, operation is more convenient, high-efficient, it is suitble to a variety of reaction substrates, and catalyst being capable of recycling and reusing.Compared with prior art, the nanometer copper oxide catalyst that the present invention uses simply easily is made, and performance is stablized, and catalytic effect is good and can recycle；Raw material benzoxazoles and terminal alkyne are reacted, and reaction condition is mild, are not needed using noble metal or strong pollution metal reagent；This reaction system is low in cost, is simple and efficient, environmental-friendly, can synthesize the 2- phenyl benzoxazoles class compound of high yield, be conducive 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- phenyl benzoxazoles class compound
Method is catalyzed preparation 2- phenyl benzoxazoles class compound using Nanometer Copper.
Background technique
In organic chemistry research, heterocycle compound is an important component of organic chemistry filed, Er Qieqi
Very extensive 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, in medicine using very universal,
It is increasingly becoming the main source of medicine.Scientist also is dedicated to developing multiple heterocycles probing into heterocycle and react with alkynes in recent years
Research for medicine, biochemistry etc..The following are part heterocyclic drug structural formulas:
In document report 2- phenyl benzoxazoles class compound synthetic method mainly include the following types:
(1) 2010 year Toshiaki Murai seminar holds the mixing of axis 1,10- Phen cationic palladium using one and urges
Agent is catalyzed heterocycle and iodobenzene synthesizes 2- phenyl benzoxazoles class compound.
The method used catalyst is not only expensive but also structure is complicated.
(2) 2013 years Jiang Cheng seminars generate 2- benzene using palladium catalyst catalysis benzoxazoles and acetylenic acid reaction
Base benzoxazoles class 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- phenyl benzoxazoles class using palladium catalyst
Compound.
Zhong-Xia Wang seminar utilizes palladium metal compound for catalysis benzoxazoles and thioether reactant within (four) 2015 years
Synthesize 2- phenyl benzoxazoles substance.
Sunwoo Lee seminar utilizes palladium chtalyst, PAR-2Hg within (five) 2016 years2+Chemistry of the compound as halide ion
Sensor is to synthesize 2- phenyl benzoxazoles class compound.
The method utilizes PAR-2Hg2+Compound may be implemented as the chemical sensor of aryl iodide, aryl bromide, aryl chloride
Suzuki coupling reaction.But this Chemical sensors pollution is too big.
In conclusion prior art synthesis 2- phenyl benzoxazoles class compound method is although more, but these method bases
Complicated ligand 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 too long, and reaction yield is lower；The compound pollution that some are used is very strong, is not suitable for
A large amount of industrial productions.More importantly this kind of reaction is mostly catalyst using the noble metals such as palladium, reaction cost costly and
And not can be recycled, it is not suitable for industrial production.
Therefore it provides a kind of novel method for synthesizing of 2- phenyl benzoxazoles class compound is necessary.
Summary of the invention
The purpose of the present invention is to provide a kind of synthetic method of 2- phenyl benzoxazoles class compound, utilization is nano oxidized
Copper catalysis benzoxazoles and end-group alkyne directly react preparation 2- phenyl benzoxazoles class compound, and synthetic method is simple, and raw material is easy
, at low cost, operation is more convenient, and it is high-efficient, it is suitble to a variety of reaction substrates, and catalyst being capable of recycling and reusing.
The present invention also provides a kind of 2- phenyl benzoxazoles class compounds, are obtained using the above method.
A kind of synthetic method of 2- phenyl benzoxazoles class compound provided by the invention, comprising the following steps:
A, after mixing catalyst, benzoxazoles, terminal alkyne, oxide and alkali, solvent is added, in oxygen atmosphere,
Heating stirring back flow reaction；
B, after reaction, product obtains 2- phenyl benzo by column chromatographic isolation and purification after extraction, drying, concentration
Dislike azole compounds.
Benzoxazoles, terminal alkyne, catalyst, oxide, alkali molar ratio are 1:1.2-1.5:0.15-0.2 in step A:
1:2.
The concentration of benzoxazoles in a solvent is 0.1mmol/mL in step A.
Relative to the benzoxazoles of 0.2mmol, 0.24-0.3mmol of terminal alkyne dosage, the oxide dosage
0.2mmol, the base amount 0.4mmol, the solvent usage 2mL；Catalyst amount is the 15%- of benzoxazoles dosage
20%.
Terminal alkyne structural formula described in step A are as follows:
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.
Benzoxazoles structural formula described in step A are as follows:
Wherein R2Selected from 5-H, 5-CH3, 5-Cl or 6-CH3In any one.
Catalyst described in step A is shuttle shape nano cupric oxide, flake nano copper oxide, appointing in particle nano cupric oxide
It anticipates one kind, can recycle and be recycled.The catalyst of different-shape all can preferably promote the synthesis of product in this reaction,
Wherein flake nano catalyst effect is especially pronounced.
Various catalyst specific in step A the preparation method is as follows:
It takes the distilled water of 40mL to be added in 100mL beaker, weighs the Cu (CH of 0.3194g3COO)2·H2O solid is placed in
In beaker, made it dissolve in the case where 30 DEG C of magnetic agitations, then be slowly dropped into the NH of 1M3·H2O solution adjusts pH value, will burn
Cup is put in baking oven with preservative film package, is reacted under the conditions of 65 DEG C and is cooled to room temperature for 24 hours, then respectively with distilled water and anhydrous
Ethyl alcohol respectively cleans twice, separation centrifugation, 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-
Middle pH 7 is answered to obtain shuttle shape nano cupric oxide；PH 8.5, flake nano copper oxide.
The preparation method of particle nanometer CuO in step A: the Cu (CH of 0.4525g is taken3COO)2It is dissolved in 50mL dehydrated alcohol,
It is placed in the polytetrafluoroethylene (PTFE) autoclave of capacity 60mL to its dissolution and reacts 20h under the conditions of 150 DEG C, be cooled to room temperature, then
Difference 2 times and washes of absolute alcohol 3 times wash with distilled water, separation centrifugation is dried in vacuo to obtain black powder under room temperature.
Heating stirring back flow reaction described in step A specifically: 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
Kind.
It is any one in silver oxide, silver carbonate, silver nitrate or silver acetate described in oxide in step A.
Step B specifically: extract products therefrom petroleum ether and saturated salt solution, anhydrous magnesium sulfate is dry, depressurizes dense
Contracting, obtains crude product, using petrol ether/ethyl acetate as solvent, obtains 2- phenyl benzoxazoles class chemical combination by column chromatography for separation
Object.
Wherein, the volume ratio of petroleum ether and ethyl acetate is 100:1.
A kind of 2- phenyl benzoxazoles class compound provided by the invention, synthesizes to obtain using the above method.
Preferably, the synthetic method of the 2- phenyl benzoxazoles class compound, comprising the following steps:
A, by 0.03mmol flake nano copper oxide, 0.2mmol benzoxazoles, 0.3mmol terminal alkyne, 0.2mmol oxygen
Change silver, 0.4mmol cesium carbonate, dimethyl sulfoxide (DMSO) 2mL is added, is stirred at reflux under conditions of oxygen atmosphere, 150 DEG C anti-
Answer 11h；
B, product obtains 2- phenyl benzoxazoles class by petroleum ether column chromatographic isolation and purification after extraction, drying, concentration
Compound.
Mechanism of the present invention is as follows: first under the assistance of Ag (I), phenylacetylene and nano cupric oxide form phenylacetylene base oxidation
Copper, due to the effect of oxygen, two molecule alkynes carbon are oxidized to diketone to form intermediate product, and then the CO of two equivalents is extracted
It is intermediate and then due to phenyl copper oxide electrophilic attack benzoxazoles to form intermediary to form phenyl copper oxide
Product restores elimination and forms arylated products and nano cupric oxide.We also did nano cupric oxide recovery experiment, experiment knot
Fruit shows that multiple recovery experiment, yield are still very high.
Compared with prior art, the nanometer copper oxide catalyst that the present invention uses simply easily is made, and performance is stablized, catalytic effect
Well and it can recycle；Raw material benzoxazoles and terminal alkyne are reacted, and reaction condition is mild, are not needed using noble metal
Or strong pollution metal reagent；This reaction system is low in cost, is simple and efficient, environmental-friendly, can synthesize the 2- benzene of high yield
Base benzoxazoles class compound, is conducive to industrial production.
Detailed description of the invention
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.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood 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,
Benzoxazoles, 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- phenyl benzoxazoles class compound, comprising the following steps:
A, weigh respectively 0.03mmol flake nano copper oxide, 0.2mmol benzoxazoles, 0.3mmol phenylacetylene,
Dimethyl sulfoxide (DMSO) 2mL is added, under conditions of oxygen atmosphere, 150 DEG C in 0.2mmol silver oxide, 0.4mmol cesium carbonate
It is stirred at reflux reaction 9h；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration is made solvent column chromatography for separation with petrol ether/ethyl acetate (volume ratio 100:1) and is purified
White solid, that is, 2- phenyl 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- phenyl benzoxazoles class compound, comprising the following steps:
A, 0.03mmol shuttle shape nano cupric oxide, 0.2mmol 5- methylbenzoxazole, 0.3mmol3- chlorobenzene are weighed respectively
Dimethyl sulfoxide (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of item in acetylene, 0.2mmol silver oxide, 0.4mmol cesium carbonate
Reaction 11h is stirred at reflux under part；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration is made solvent column chromatography for separation with petrol ether/ethyl acetate (volume ratio 100:1) and is purified
White solid, that is, 2- (3- chlorphenyl) -5- methylbenzoxazole, 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- phenyl benzoxazoles class compound, comprising the following steps:
A, 0.03mmol particle nano cupric oxide, 0.2mmol benzoxazoles, 0.3mmol 4- ethoxybenzene second are weighed respectively
Dimethyl sulfoxide (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition in alkynes, 0.2mmol silver oxide, 0.4mmol cesium carbonate
Under be stirred at reflux reaction 11h；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration makees solvent column chromatography for separation with petrol ether/ethyl acetate (100:1) and purifies white solid
Body, that 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- phenyl benzoxazoles class compound, comprising the following steps:
A, weigh respectively 0.03mmol flake nano copper oxide, 0.2mmol benzoxazoles, 0.3mmol phenylacetylene,
Dimethyl sulfoxide (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition in 0.2mmol silver oxide, 0.4mmol potassium hydroxide
Under be stirred at reflux reaction 11h；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration makees solvent column chromatography for separation with petrol ether/ethyl acetate (100:1) and purifies white solid
Body, that is, 2- phenyl 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- phenyl benzoxazoles class compound, comprising the following steps:
A, 0.03mmol flake nano copper oxide, 0.2mmol benzoxazoles, 0.3mmol 4- methylbenzene second are weighed respectively
Dimethyl sulfoxide (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition in alkynes, 0.2mmol silver carbonate, 0.4mmol cesium carbonate
Under be stirred at reflux reaction 11h；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration is made solvent column chromatography for separation with petrol ether/ethyl acetate (volume ratio 100:1) and is purified
White solid, that 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- phenyl benzoxazoles class compound, comprising the following steps:
A, 0.03mmol flake nano copper oxide, 0.2mmol benzoxazoles, 0.3mmol 4- tert-butyl benzene second are weighed respectively
Dimethyl sulfoxide (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of condition in alkynes, 0.2mmol silver acetate, 0.4mmol cesium carbonate
Under be stirred at reflux reaction 11h；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration is made solvent column chromatography for separation with petrol ether/ethyl acetate (volume ratio 100:1) and is purified
White solid, that 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- phenyl benzoxazoles class compound, comprising the following steps:
A, 0.03mmol flake nano copper oxide, 0.2mmol benzoxazoles, 0.3mmol 2- methoxybenzene second are weighed respectively
Dimethyl sulfoxide (DMSO) 2mL is added, in oxygen atmosphere, 150 DEG C of item in alkynes, 0.2mmol silver oxide, 0.4mmol sodium hydroxide
Reaction 11h is stirred at reflux under part；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration makees solvent column chromatography for separation with petrol ether/ethyl acetate (100:1) and purifies white solid
Body, that 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- phenyl benzoxazoles class compound, comprising the following steps:
A, 0.03mmol flake nano copper oxide, 0.2mmol benzoxazoles, 0.3mmol 4-n amylbenzene second are weighed respectively
N,N-Dimethylformamide (DMF) 2mL, in oxygen atmosphere, 150 DEG C is added in alkynes, 0.2mmol silver oxide, 0.4mmol cesium carbonate
Under conditions of be stirred at reflux reaction 11h；
B, it is cooled to room temperature after stopping reaction, is extracted 3-5 times with ethyl acetate and saturated salt solution, and by gained organic phase
Dry with anhydrous magnesium sulfate, concentration makees solvent column chromatography for separation with petrol ether/ethyl acetate (100:1) and purifies white solid
Body, that is, 2- (4-n amyl phenyl) benzoxazoles, 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 (7)
1. a kind of synthetic method of 2- phenyl benzoxazoles class compound, which is characterized in that the synthetic method includes following step
It is rapid:
A, after mixing catalyst, benzoxazoles, terminal alkyne, oxide and alkali, solvent is added, in oxygen atmosphere, heating
It is stirred at reflux reaction；
B, after reaction, product obtains 2- phenyl benzoxazoles by column chromatographic isolation and purification after extraction, drying, concentration
Class compound；
Catalyst described in step A is shuttle shape nano cupric oxide, and flake nano copper oxide is any one in particle nano cupric oxide
Kind；
Terminal alkyne structural formula described in step A are as follows:
, 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；
Benzoxazoles structural formula described in step A are as follows:
, wherein R2Selected from 5-H, 5-CH3, 5-Cl or 6-CH3In any one.
2. the synthetic method of 2- phenyl benzoxazoles class compound according to claim 1, which is characterized in that in step A
Benzoxazoles, terminal alkyne, catalyst, oxide, alkali molar ratio are 1:1.2-1.5:0.15-0.2:1:2.
3. the synthetic method of 2- phenyl benzoxazoles class compound according to claim 1 or 2, which is characterized in that step A
Described in heating stirring back flow reaction specifically: be stirred at reflux under conditions of 140-150 DEG C reaction 9-11h.
4. the synthetic method of 2- phenyl benzoxazoles class compound according to claim 1 or 2, which is characterized in that step A
Described in alkali be sodium hydroxide, potassium hydroxide, potassium carbonate or cesium carbonate in any one.
5. the synthetic method of 2- phenyl benzoxazoles class compound according to claim 1 or 2, which is characterized in that step A
Described in solvent be any one or two kinds in N,N-dimethylformamide DMF or dimethyl sulfoxide DMSO.
6. the synthetic method of 2- phenyl benzoxazoles class compound according to claim 1 or 2, which is characterized in that step A
It is any one in silver oxide, silver carbonate, silver nitrate or silver acetate described in middle oxide.
7. the synthetic method of 2- phenyl benzoxazoles class compound according to claim 1 or 2, which is characterized in that step B
Specifically: products therefrom petroleum ether and saturated salt solution are extracted, anhydrous magnesium sulfate is dry, and it is concentrated under reduced pressure, obtains crude product, with
Petrol ether/ethyl acetate is solvent, obtains 2- phenyl benzoxazoles class compound by column chromatography for separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710652421.6A CN107382895B (en) | 2017-08-02 | 2017-08-02 | A kind of synthetic method of 2- phenyl benzoxazoles class compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710652421.6A CN107382895B (en) | 2017-08-02 | 2017-08-02 | A kind of synthetic method of 2- phenyl benzoxazoles class compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107382895A CN107382895A (en) | 2017-11-24 |
| CN107382895B true CN107382895B (en) | 2019-09-27 |
Family
ID=60344556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710652421.6A Active CN107382895B (en) | 2017-08-02 | 2017-08-02 | A kind of synthetic method of 2- phenyl benzoxazoles class compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107382895B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605341A (en) * | 2022-04-25 | 2022-06-10 | 安徽师范大学 | Benzisoxazole compound and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014122811A1 (en) * | 2013-02-07 | 2014-08-14 | 国立大学法人名古屋大学 | Coupling method and method for producing aromatic group-substituted heterocyclic compound using said coupling method |
| CN104086504A (en) * | 2014-07-04 | 2014-10-08 | 太仓博亿化工有限公司 | Synthetic method of 2-substituted benzoxazole |
| US20160068482A1 (en) * | 2013-03-15 | 2016-03-10 | The Regents Of The University Of California | Carbamate derivatives of lactam based n-acylethanolamine acid amidase (naaa) inhibitors |
-
2017
- 2017-08-02 CN CN201710652421.6A patent/CN107382895B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014122811A1 (en) * | 2013-02-07 | 2014-08-14 | 国立大学法人名古屋大学 | Coupling method and method for producing aromatic group-substituted heterocyclic compound using said coupling method |
| US20160068482A1 (en) * | 2013-03-15 | 2016-03-10 | The Regents Of The University Of California | Carbamate derivatives of lactam based n-acylethanolamine acid amidase (naaa) inhibitors |
| CN104086504A (en) * | 2014-07-04 | 2014-10-08 | 太仓博亿化工有限公司 | Synthetic method of 2-substituted benzoxazole |
Non-Patent Citations (3)
| Title |
|---|
| The palladium-catalyzed tandem decarboxylation, carbon–carbon triple bond oxidation and decarbonylative arylation of the benzoxazole C–H bond;Dongfang Liu et al;《RSC Advances》;20130423;第3卷;第9193-9196页，尤其是第9194页Fig.2以及Supporting Information第S2页 * |
| 唑类C-H官能团化研究;李倩;《安徽师范大学硕士学位论文》;20181218;第1-105页 * |
| 纳米铜催化杂环C-H芳基化反应研究;曾庆龙等;《第十六届全国金属有机化学学术讨论会论文集》;20101022;第13页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107382895A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Morimoto et al. | A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides | |
| CN108774121B (en) | Method for preparing alpha-aryl-beta-trifluoromethyl ketone compound by visible light catalysis | |
| Pagoti et al. | Reduction of organic azides to amines using reusable Fe 3 O 4 nanoparticles in aqueous medium | |
| Yeom et al. | Silver (I)-catalyzed direct route to isoquinoline-N-oxides | |
| Wang et al. | Transition-Metal-Free Synthesis of Ynones via Decarboxylative Alkynylation of α-Keto Acids under Mild Conditions | |
| Hajipour et al. | Dimeric ortho-palladated complex of 2, 3-dimethoxybenzaldehyde oxime catalyzed Suzuki–Miyaura cross-coupling reaction under microwave irradiation | |
| Beladhria et al. | Benzenesulfonyl Chlorides: Alternative Coupling Partners for Regiocontrolled Palladium-Catalyzed Direct Desulfitative 5-Arylation of Furans | |
| Zeng et al. | Oxygen-atom insertion of NHC–copper complex: The source of oxygen from N, N-dimethylformamide | |
| Zhang | Advances in trifluoromethylation or trifluoromethylthiolation with copper CF _ 3 CF 3 or SCF _ 3 SCF 3 complexes | |
| CN106518663B (en) | A kind of preparation method of alpha-acyloxy ketone compound | |
| CN107382895B (en) | A kind of synthetic method of 2- phenyl benzoxazoles class compound | |
| Trongsiriwat et al. | Palladium‐Catalyzed Allylic Alkylation of 2‐Aryl‐1, 3‐Dithianes, an Umpolung Synthesis of β, γ‐Unsaturated Ketones | |
| CN103172480B (en) | Method for preparing iodo aromatic hydrocarbon | |
| Yin et al. | Catalyst-free C–S/C–O bond formation: synthesis of novel 4-thio-substituted 2-aryl-4H-chromenes from easily available 2-hydroxychalcones | |
| Gold et al. | Microwave irradiation as a high-speed tool for activation of sluggish aryl chlorides in Grignard reactions | |
| Zhao et al. | Copper-catalyzed decarboxylative hydroboration of phenylpropiolic acids under ligand-free or both ligand-and base-free conditions | |
| CN105367399B (en) | A kind of preparation method of 9,10 luxuriant and rich with fragrance quinones | |
| Yadav et al. | Base-mediated synthesis of imines and amines from N-phenylureas and alcohols | |
| Yadav et al. | Elemental Iodine-CatalyzedCoupling of Alkynylsilanes with Acid Chlorides: A Facile Synthesisof α, β-Acetylenic Ketones | |
| CN106631718B (en) | A kind of synthetic method of asymmetric conjugation diine | |
| CN110041274B (en) | Method for preparing 5-fluoroalkyl triazole compound by air oxidation multi-component one-pot method | |
| Dabdoub et al. | Synthesis of (Z)-1-Organylthiobut-1-en-3-ynes: Hydrothiolation of Symmetrical and Unsymmetrical Buta-1, 3-diynes | |
| Kumaravel et al. | Application of bisphosphomide-palladium (II) pincer complex in Suzuki–Miyaura cross-coupling reaction under microwave irradiation | |
| CN108383754B (en) | Preparation method and application of aryl oxime ester compound | |
| Kawano et al. | Iodoarene-mediated one-pot preparation of 2, 4, 5-trisubstituted oxazoles from ketones |
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 |