CN105289663A - Magnetically-recoverable GO/Fe3O4-CuI catalyst and preparation method and application thereof - Google Patents
Magnetically-recoverable GO/Fe3O4-CuI catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a magnetically-recoverable GO/Fe3O4-CuI catalyst and a preparation method and application thereof. The amount of supported Cu + in the GO/Fe3O4-CuI catalyst is 10-11% by weight, the GO/Fe3O4-CuI catalyst is prepared by adding graphene oxide powder into 2-pyrrolidone, then adding a ferric triacetylacetonate solution after ultrasonic processing, performing stirring and reflux reaction to produce a black precipitate GO/Fe3O4, adding the black precipitate and CuI into anhydrous ethanol and performing magnetic stirring reflux, the prepared GO/Fe3O4-CuI catalyst can be used for catalytic reaction of o-halogen benzamide and amino acid to generate a quinazolinone compound. Compared with the prior art, the catalyst is simple in preparation, high in catalytic activity and high in recovery rate, and the high catalytic performance of the recovered catalyst is still kept.
Description
Technical field
The invention belongs to Industrial Catalysis and organic compound synthesis field, what relate to is a kind of application of novel magnetic catalyst, especially relate to a kind of can the GO/Fe of magnetic recovery
3o
4-CuI Catalysts and its preparation method and this catalyst are catalyzing and synthesizing the application of quianzolinones.
Background technology
Quinazolinone is extensively present in natural products as skeleton structure.As Luotonin is present in camel wormwood artemisia, 2-melthyl-4 (3H)-quinazolinone is present in Bacillus cercus, 2-(4-hydroxybutyl)-quinazolin-4-one is present in herbaceous plant Changshan, Bouchardatine is present in quianzolinones in rutaceae and has biologically active and medical value, as they can be used for somnifacient, sedative, antalgesic, antitussive, anti-inflammatory agent, antimicrobial, antineoplastic, antidiabetic and anticonvulsant etc.In addition be that the medicine of skeleton structure is used for the treatment of cancer in clinical trial with quinazolinone.
The method of current synthesis quianzolinones is a lot, the relevant report of the catalyst wherein reacted as such compou nd synthesis with cuprous salt or cupric salt is more popular in recent years, mantoquita activated centre Nature comparison as homogeneous catalyst is single, catalytic efficiency is higher, side reaction is less, and the mechanism of catalytic reaction is general comparatively simple, but however, for use and the industrialization promotion of homogeneous catalyst, still there is a lot of problem, wherein catalyst difficulty reclaims is a great problem that current scientific domain faces.If but mantoquita load is prepared into heterogeneous catalysis on a catalyst support, go to catalyze and synthesize quianzolinones, after reaction terminates, catalyst is just easier to be separated with reaction system, realize catalyst recovery recycling, meet the requirement of Green Chemistry to chemical reaction.
Research in recent years about graphene oxide is very burning hot, due to graphene oxide, to have specific area large, superior electric conductivity and surface are containing abundant oxy radical, as hydroxyl, carboxyl, ether etc., the modification existing for surface of graphene oxide of these oxy radicals provides possibility, often the graphene oxide of load solid titania is used as photochemical catalyst in lithium battery preparation field at present, strengthen current density, in electrochemistry, achieve very large achievement.Scientific achievement based on the older generations can find, the surface of graphene oxide not only can the solid-state oxide particle of load, oxy radical abundant for the surface of graphene oxide can also be passed through coordination, can to the slaine with catalytic activity various in the coordination of graphene oxide top layer.Nowadays many chemists more wish these exceptional functions of graphene oxide to be played in organic chemical synthesis reaction, and being transformed into callable environmentally friendly support type graphene oxide catalyst, is an important directions of green chemistry.
Summary of the invention
Object of the present invention is exactly provide a kind of catalyst easy recycling to overcome defect that above-mentioned prior art exists, and keep efficient catalytic performance can the GO/Fe of magnetic recovery
3o
4-CuI Catalysts and its preparation method and application.
Object of the present invention can be achieved through the following technical solutions: a kind of can the GO/Fe of magnetic recovery
3o
4-CuI catalyst, is characterized in that, this catalyst is CuI doped F e
3o
4back loading on graphene oxide, wherein Cu
+load capacity be 10wt% ~ 11wt%.
A kind of can the GO/Fe of magnetic recovery
3o
4the preparation method of-CuI catalyst, is characterized in that, the method comprises the following steps:
(1) graphene oxide powder is joined 2-Pyrrolidone, ultrasonic process 2 ~ 4h obtains mixture in a nitrogen atmosphere;
(2) add hot mixt, and drip praseodynium ferrous solution under mechanical stirring, stirring and refluxing, reaction, obtains black precipitate GO/Fe
3o
4;
(3) by black precipitate GO/Fe
3o
4after magnetic recovery, washing, drying, obtain GO/Fe
3o
4product;
(4) by GO/Fe
3o
4product and CuI add in absolute ethyl alcohol, magnetic stirring backflow in a nitrogen atmosphere, by magnetic recovery black solid, then wash, after drying, namely obtain catalyst GO/Fe
3o
4-CuI.
The mass volume ratio of the graphene oxide described in step (1) and 2-Pyrrolidone is (1 ~ 2) g:300mL.
Praseodynium ferrous solution described in step (2) is the solution of praseodynium dissolved ferric iron in 2-Pyrrolidone, and its concentration is 0.06 ~ 0.2mol/L; Fe
3+be 20mmol:1g with the rate of charge of graphene oxide;
Praseodynium ferrous solution and graphene oxide reaction temperature be 185 ~ 195 DEG C, the reaction time is 8 ~ 12h.
GO/Fe described in step (4)
3o
4be 2:1 with the addition mass ratio of CuI, reaction temperature is 75 ~ 85 DEG C, and the reaction time is 8 ~ 10h;
Step (3) and the washing described in step (4) are for adopting absolute ethanol washing repeatedly, and drying is vacuum drying at 40 ~ 50 DEG C.
A kind of can the GO/Fe of magnetic recovery
3o
4the application of-CuI catalyst on synthesis quianzolinones, is characterized in that, comprise the following steps:
A () is by GO/Fe
3o
4-CuI, amino acid, cesium carbonate, adjacent halogen benzoyl amine and ethylene glycol/methyl-sulfoxide, at 110 ~ 130 DEG C, mix and blend backflow 5 ~ 7h;
B reacted mixed solution magnetic recovery is obtained black solid by (), after washing drying, and the GO/Fe be recycled
3o
4-CuI catalyst;
C the ethyl acetate of residual mixed liquor volume ratio 1:1 after magnetic recovery in step (b) and the extractant of water extract by (), be separated organic phase pillar layer separation and obtain quianzolinones.
In step (a), the structural formula of described adjacent halogen benzoyl amine is as follows:
Wherein, R
1be selected from H, F or CH
3in one, R
2for H or F;
Described amino acid whose structural formula is as follows:
Wherein, R
3be selected from CH
2cH
2cH
3, CH (CH
3)
2, CH
2cH (CH
3)
2, CH
2(Ph) one or in Ph.
Adjacent halogen benzoyl amine described in step (a), the mol ratio of amino acid, cesium carbonate is 1:(2 ~ 3): (2 ~ 3), described ethylene glycol/methyl-sulfoxide is the ethylene glycol of volume ratio 1:60 and the mixture of methyl-sulfoxide, and its consumption is according to the interpolation 10 ~ 15mL of the adjacent halogen benzoyl amine of every 1mmol; Described GO/Fe
3o
4the consumption of-CuI is according to the interpolation 0.0150g ~ 0.0200g of the adjacent halogen benzoyl amine of every 1mmol.
As optimum condition, the adjacent halogen benzoyl amine described in step (a), the mol ratio of amino acid, cesium carbonate is 1:3:3, and the consumption of ethylene glycol/methyl-sulfoxide is according to the interpolation 10mL of the adjacent halogen benzoyl amine of every 1mmol; Described GO/Fe
3o
4the consumption of-CuI is according to the interpolation 0.0200g of the adjacent halogen benzoyl amine of every 1mmol.
The drying of washing described in step (b) is with absolute ethyl alcohol and washs for several times, and 45 DEG C of vacuum drying are reclaimed.
GO/Fe
3o
4-CuI catalyzes and synthesizes the reaction equation that amino acid and adjacent halogen benzoyl amine synthesizes quianzolinones:
In above-mentioned reaction equation, R
1be selected from H, F, CH
3in one, R
2be selected from H, the one in F, R
3be selected from (CH
3)
2, CH
2cH
2cH
3, CH
2cH (CH
3)
2, CH
2(Ph) one, in Ph.
Compared with prior art, catalyst GO/Fe of the present invention
3o
4the preparation of-CuI is simple, at GO/Fe
3o
4-CuI catalyzes and synthesizes in the method for quianzolinones, has catalytic performance effectively, and catalyst can easily be reclaimed by permanent magnet adsorbing, and recycling still remains efficient catalytic performance.
Accompanying drawing explanation
Fig. 1 is the catalyst GO/Fe in embodiments of the invention 1
3o
4the infrared spectrum analysis figure (IR) of-CuI;
Fig. 2 is the catalyst GO/Fe in embodiments of the invention 1
3o
4the X-ray diffractogram (XRD) of-CuI;
Fig. 3 is the catalyst GO/Fe in embodiments of the invention 1
3o
4the scanning electron microscope (SEM) photograph of-CuI.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Magnetic GO/Fe
3o
4the preparation of-CuI catalyst
(1) graphene oxide powder 1g is added in the 2-Pyrrolidone of 300ml, ultrasonic 4 hours in a nitrogen atmosphere;
(2) after ultrasonic, the mixture in step (1) is heated to 190 DEG C, is added dropwise to the 2-Pyrrolidone solution that concentration is 0.1mol/L praseodynium iron under mechanical agitation, makes Fe
3+be 20mmol:1g, stirring and refluxing 10h with the rate of charge of graphene oxide;
(3) by the reacted black precipitate GO/Fe in step (2)
3o
4magnetic recovery, with absolute ethanol washing repeatedly, 45 DEG C of vacuum drying;
(4) by the GO/Fe of drying
3o
4be mass ratio 2:1 with CuI with rate of charge, add in absolute ethyl alcohol, in a nitrogen atmosphere 80 DEG C of magnetic stirrings backflows 8h, black solid GO/Fe
3o
4-CuI magnetic recovery, with absolute ethanol washing several, 45 DEG C of vacuum drying, the GO/Fe obtained
3o
4-CuI catalyst ICP-AES tests, and obtains Cu
+load capacity be 10.1% (mass ratio).
And obtained catalyst is detected, result is specific as follows.
Fig. 1 shows the obtained catalyst GO/Fe of above-described embodiment 1
3o
4-CuI and simple graphene oxide GO, GO/Fe
3o
4infrared spectrum analysis, can find out that peak value is at 3370cm
-1, 1730cm
-1the stretching vibration .1622cm of O-H, C=O in COOH
-1, 1230cm
-1and 1056cm
-1place is C=C, the C-O of carbonyl and the key chattering of alkoxy C-O on aromatic rings.580cm
-1there is the vibration of obvious Fe-O at place, and Fe is described
3o
4load on graphene oxide.By 800cm
-1to 1000cm
-1between the change of INFRARED ABSORPTION can judge that CuI has loaded on graphite oxide.
Fig. 2 shows the obtained catalyst GO/Fe of above-described embodiment 1
3o
4-CuI and independent GO, Fe
3o
4, CuI XRD spectrum, by carrying out the change of the XRD spectra before and after CuI load on graphene oxide, can find at 25.4 °, 41.6 °, 49.2 ° there is the characteristic peak of CuI, can prove CuI load GO/Fe
3o
4on.
In Fig. 3, a, b respectively illustrate the catalyst GO/Fe under 100 μm and 5 μm
3o
4the scanning electron microscope (SEM) photograph of-CuI, c and d respectively illustrates GO/Fe
3o
4with the scanning electron microscope (SEM) photograph of GO, be distributed in GO/Fe while CuI uniform particles can be found out
3o
4surface, can prove CuI load GO/Fe
3o
4on.
Embodiment 2
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 2-iodobenzamide and valine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol valine, 0.9mmol cesium carbonate, 0.3mmol2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic absorption reclaims and obtains black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and the structural formula of product is:
Productive rate is 72%, by the catalyst GO/Fe of above-mentioned reaction
3o
4after-CuI magnetic recovery, react under identical reaction conditions again, so, repeat twice, the productive rate of obtained quianzolinones is respectively 73%, 70%, can draw the result that catalyst circulation uses, this catalyst can realize heavily recycling, and decreases the waste of catalyst and the pollution to environment.
The product obtained through use NMR collect this product hydrogen spectrum and carbon compose carry out setting analysis, re-use high-resolution and quality analysis carried out to this material, obtain following data:
1HNMR(400MHz,CDCl
3)δ11.35(s,1H),8.37–8.25(m,1H),7.86–7.69(m,2H),7.53–7.44(m,1H),3.06(dp,J=13.5,6.8Hz,1H),1.47(d,J=7.0Hz,6H).
13CNMR(101MHz,DMSO-d
6)δ162.40,162.03,149.35,134.72,127.44,126.42,126.13,121.40,33.77,20.85.HRMS-ESI:m/zcalcdforC
11H
12N
2O[M+H]
+:189.0950,found189.1019。
Embodiment 3
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 2-iodobenzamide and norvaline synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol norvaline, 0.9mmol cesium carbonate, 0.3mmol2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 74%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,CDCl
3)δ12.06(s,1H),8.40–8.27(m,1H),7.84–7.78(m,1H),7.77–7.73(m,1H),7.57–7.44(m,1H),2.82(dd,J=16.0,8.1Hz,2H),1.96(dt,J=14.5,7.3Hz,2H),1.12(t,J=7.4Hz,3H)..
13CNMR(101MHz,CDCl
3)δ164.33,156.81,149.48,134.81,127.21,126.32(d,J=10.9Hz),126.24–126.16(m),120.52,37.76,21.04,13.96(d,J=39.2Hz).HRMS-ESI:m/zcalcdforC
11H
12N
2O[M+H]
+:189.0950,found189.1009。
Embodiment 4
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 2-iodobenzamide and leucine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol leucine, 0.9mmol cesium carbonate, 0.3mmol2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 90%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,CDCl
3)δ11.95(d,J=57.7Hz,1H),8.30(d,J=8.0Hz,1H),7.82–7.69(m,1H),7.53–7.43(m,1H),2.68(d,J=7.4Hz,2H),2.41–2.28(m,1H),1.12–1.03(m,6H).
13CNMR(101MHz,CDCl
3)δ164.34,156.26,149.47,134.84,127.27,126.23,120.44,44.81,29.56(d,J=33.7Hz),28.03,22.40.HRMS-ESI:m/zcalcdforC
12H
14N
2O[M+H]
+:203.1106,found203.1166。
Embodiment 5
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 2-iodobenzamide and 2-amino-2-phenylacetic acid synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol2-amino-2-phenylacetic acid, 0.9mmol cesium carbonate, 0.3mmol2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 61%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,CDCl
3)δ11.87(s,1H),8.35(t,J=8.3Hz,1H),8.30(dt,J=7.1,3.6Hz,2H),7.91–7.78(m,2H),7.67–7.57(m,3H),7.57–7.50(m,1H).
13CNMR(101MHz,DMSO-d
6)δ162.69,152.77,149.21,135.08,133.18,131.86,129.07,128.22–128.08(m),127.95–127.81(m),127.06,126.32,121.46.HRMS-ESI:m/zcalcdforC
14H
10N
2O[M+H]
+:223.0793,found223.0850。
Embodiment 6
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 2-iodobenzamide and phenylalanine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol phenylalanine, 0.9mmol cesium carbonate, 0.3mmol2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 79%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,CDCl
3)δ11.87(s,1H),8.35(t,J=8.3Hz,1H),8.30(dt,J=7.1,3.6Hz,2H),7.91–7.78(m,2H),7.67–7.57(m,3H),7.57–7.50(m,1H).
13CNMR(101MHz,DMSO-d
6)δ162.69,152.77,149.21,135.08,133.18,131.86,129.07,128.22–128.08(m),127.95–127.81(m),127.06,126.32,121.46.HRMS-ESI:m/zcalcdforC
14H
10N
2O[M+H]
+:223.0793,found223.0850。
Embodiment 7
By catalyst GO/Fe obtained in embodiment 1
3o
4the fluoro-2-iodobenzamide of-CuI catalysis 4-and valine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4the fluoro-2-iodobenzamide of-CuI, 0.9mmol valine, 0.9mmol cesium carbonate, 0.3mmol4-and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 79%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1hNMR (400MHz, CDCl
3) δ 11.73 (s, 1H), 8.36 (ddd, J=15.0,11.7,7.7Hz, 1H), 7.44 – 7.35 (m, 1H), 7.21 (tt, J=16.8,8.4Hz, 1H), 3.15 – 3.00 (m, 1H), 1.46 (t, J=12.4Hz, 6H).
13cNMR (101MHz, CDCl
3) δ 165.56 – 165.35 (m), 163.52,162.20,151.77 (d, J=13.2Hz), 128.95 (d, J=10.7Hz), 117.42,115.19 (d, J=23.6Hz), 112.78 (d, J=21.7Hz), 34.94,29.73,20.39.HRMS-ESI:m/zcalcdforC
11h
11fN
2o [M+H]
+: 207.0855, found207.0912 (the same).
Embodiment 8
By catalyst GO/Fe obtained in embodiment 1
3o
4the fluoro-2-iodobenzamide of-CuI catalysis 4-and leucine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4the fluoro-2-iodobenzamide of-CuI, 0.9mmol leucine, 0.9mmol cesium carbonate, 0.3mmol4-and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 86%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,DMSO-d
6)δ12.30(s,1H),8.33–8.01(m,1H),7.55–7.18(m,1H),2.48(d,J=7.3Hz,2H),2.18(dt,J=13.7,6.7Hz,1H),0.93(d,J=6.6Hz,6H).
13CNMR(101MHz,DMSO-d
6)δ167.66–166.98(m),161.58,158.89,152.00–151.02(m),129.27(d,J=11.0Hz),119.03–117.07(m),114.98(d,J=23.6Hz),112.32(d,J=21.4Hz),43.79,27.53,22.58.HRMS-ESI:m/zcalcdforC
12H
13FN
2O[M+H]
+:221.1012,found221.1069。
Embodiment 9
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 5-methyl-2-iodobenzamide and valine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol valine, 0.9mmol cesium carbonate, 0.3mmol5-methyl-2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 40%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,DMSO-d
6)δ12.06(s,1H),7.88(s,1H),7.60(dd,J=8.3,1.6Hz,1H),7.51(d,J=8.3Hz,1H),2.87(dp,J=13.5,6.6Hz,2H),2.16(s,3H),1.25(t,J=5.4Hz,6H).
13CNMR(101MHz,DMSO-d
6)δ162.34,161.09,147.34,135.97,135.93,127.30,125.50,121.14,33.68,21.22,20.85.HRMS-ESI:m/zcalcdforC
12H
14N
2O[M+H]
+:203.1106,found203.1155。
Embodiment 10
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 5-methyl-2-iodobenzamide and norvaline synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol norvaline, 0.9mmol cesium carbonate, 0.3mmol5-methyl-2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 53%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,DMSO-d
6)δ12.09(s,1H),7.87(s,1H),7.59(dd,J=8.3,1.5Hz,1H),7.50(d,J=8.3Hz,1H),2.55(dd,J=17.2,9.5Hz,2H),2.42(s,3H),1.80–1.67(m,2H),0.93(t,J=7.4Hz,3H).
13CNMR(101MHz,DMSO-d
6)δ162.21,156.82,147.42,135.97,135.89,127.13,125.50,121.00,36.75,21.21,20.66,13.97.HRMS-ESI:m/zcalcdforC
12H
14N
2O[M+H]
+:203.1106,found203.1147。
Embodiment 11
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 5-methyl-2-iodobenzamide and leucine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol leucine, 0.9mmol cesium carbonate, 0.3mmol5-methyl-2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 49%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,DMSO-d
6)δ11.64(s,1H),7.90(s,1H),7.62(dd,J=8.4,1.7Hz,1H),7.53(d,J=8.2Hz,1H),2.47(dd,J=17.6,9.8Hz,2H),2.40(s,3H),1.75–1.66(m,1H),0.12(t,J=7.6Hz,6H).
13CNMR(101MHz,DMSO-d
6)δ163.21,157.72,148.12,136.24,135.87,128.43,126.40,121.90,38.55,22.21,21.66,14.56.HRMS-ESI:m/zcalcdforC
13H
16N
2O[M+H]
+:217.1263,found217.1318。
Embodiment 12
By catalyst GO/Fe obtained in embodiment 1
3o
4-CuI catalysis 5-methyl-2-iodobenzamide and 2-amino-2-phenylacetic acid synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4-CuI, 0.9mmol2-amino-2-phenylacetic acid, 0.9mmol cesium carbonate, 0.3mmol5-methyl-2-iodobenzamide and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 49%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,DMSO-d
6)δ11.64(s,1H),7.90(s,1H),7.62(dd,J=8.4,1.7Hz,1H),7.53(d,J=8.2Hz,1H),2.47(dd,J=17.6,9.8Hz,2H),2.40(s,3H),1.75–1.66(m,1H),0.12(t,J=7.6Hz,6H).
13CNMR(101MHz,DMSO-d
6)δ163.21,157.72,148.12,136.24,135.87,128.43,126.40,121.90,38.55,22.21,21.66,14.56.HRMS-ESI:m/zcalcdforC
13H
16N
2O[M+H]
+:217.1263,found217.1318。
Embodiment 13
By catalyst GO/Fe obtained in embodiment 1
3o
4the fluoro-2-iodobenzamide of-CuI catalysis 5-and valine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4the fluoro-2-iodobenzamide of-CuI, 0.9mmol valine, 0.9mmol cesium carbonate, 0.3mmol5-and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 49%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,DMSO-d
6)δ11.64(s,1H),7.90(s,1H),7.62(dd,J=8.4,1.7Hz,1H),7.53(d,J=8.2Hz,1H),2.47(dd,J=17.6,9.8Hz,2H),2.40(s,3H),1.75–1.66(m,1H),0.12(t,J=7.6Hz,6H).
13CNMR(101MHz,DMSO-d
6)δ163.21,157.72,148.12,136.24,135.87,128.43,126.40,121.90,38.55,22.21,21.66,14.56.HRMS-ESI:m/zcalcdforC
13H
16N
2O[M+H]
+:217.1263,found217.1318。
Embodiment 14
By catalyst GO/Fe obtained in embodiment 1
3o
4the fluoro-2-iodobenzamide of-CuI catalysis 5-and leucine synthesis quianzolinones, concrete steps are:
A () is by 0.006gGO/Fe
3o
4the fluoro-2-iodobenzamide of-CuI, 0.9mmol leucine, 0.9mmol cesium carbonate, 0.3mmol5-and 3ml ethylene glycol/methyl-sulfoxide add in 50ml round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 7h at 120 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of quianzolinones of synthesis is 43%, and the product obtained is composed carry out setting analysis through being used NMR to collect the hydrogen spectrum of this product and carbon, re-uses high-resolution and carries out quality analysis to this material, obtain following data:
1HNMR(400MHz,CDCl
3)δ11.77(s,1H),7.91(dd,J=8.3,3.0Hz,1H),7.73(dd,J=9.0,4.8Hz,1H),7.54–7.47(m,1H),2.66(d,J=7.4Hz,2H),2.35–2.29(m,1H),1.07(dd,J=6.6,3.1Hz,6H).
13CNMR(101MHz,CDCl
3)δ162.17–161.39(m),155.33,136.34,129.67(d,J=8.0Hz),127.08,125.60,123.41(d,J=24.2Hz),111.04(d,J=23.3Hz),44.77(d,J=9.9Hz),27.95,21.84(d,J=108.4Hz).HRMS-ESI:m/zcalcdforC
12H
13FN
2O[M+H]
+:221.1012,found221.1072。
Embodiment 15
GO/Fe
3o
4the preparation of-CuI catalyst:
(1) graphene oxide powder is joined 2-Pyrrolidone, wherein, the mass volume ratio of graphene oxide and 2-Pyrrolidone is 1g:300mL, and ultrasonic process 2h obtains mixture in a nitrogen atmosphere;
(2) add hot mixt to 185 DEG C, and drip the praseodynium ferrous solution that concentration is 0.06mol/L under mechanical stirring, make Fe
3+compare for 20mmol:1g with the molal weight of graphene oxide, stirring and refluxing, reaction 8h, obtains black precipitate GO/Fe
3o
4;
(3) by black precipitate GO/Fe
3o
4magnetic recovery, with absolute ethanol washing repeatedly, after 40 DEG C of vacuum drying, obtain GO/Fe
3o
4product;
(4) by GO/Fe
3o
4product and CuI add in absolute ethyl alcohol with mass ratio 2:1, in a nitrogen atmosphere, in 75 DEG C of magnetic stirring and refluxing 9h, by magnetic recovery black solid, then with absolute ethanol washing repeatedly, after 40 DEG C of vacuum drying, namely obtain catalyst GO/Fe
3o
4-CuI, with ICP-AES test, obtains Cu in catalyst
+load capacity be 10wt%.
By above-mentioned obtained catalyst GO/Fe
3o
4-CuI is used for the fluoro-2-iodobenzamide of catalysis 4-and leucine synthesis quianzolinones, and concrete steps are:
A () is by 0.015gGO/Fe
3o
4the fluoro-2-iodobenzamide of-CuI, 2mmol leucine, 2mmol cesium carbonate, 1mmol4-and 12ml ethylene glycol/methyl-sulfoxide add in round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 5h at 110 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of the quianzolinones of synthesis is 88%.
Embodiment 16
A kind of can the GO/Fe of magnetic recovery
3o
4-CuI catalyst, Cu
+load capacity be 11wt%, its preparation method comprises the following steps:
(1) graphene oxide powder is joined 2-Pyrrolidone, wherein, the mass volume ratio of graphene oxide and 2-Pyrrolidone is 2g:300mL, and ultrasonic process 3h obtains mixture in a nitrogen atmosphere;
(2) add hot mixt to 195 DEG C, and drip the praseodynium ferrous solution that concentration is 0.1mol/L under mechanical stirring, make Fe
3+compare for 20mmol:1g with the molal weight of graphene oxide, stirring and refluxing reaction 12h, obtains black precipitate GO/Fe
3o
4;
(3) by black precipitate GO/Fe
3o
4magnetic recovery, with absolute ethanol washing repeatedly, after 50 DEG C of vacuum drying, obtain GO/Fe
3o
4product;
(4) by GO/Fe
3o
4product and CuI add in absolute ethyl alcohol with mass ratio 2:1, in a nitrogen atmosphere, in 85 DEG C of magnetic stirring and refluxing 10h, by magnetic recovery black solid, then with absolute ethanol washing repeatedly, after 50 DEG C of vacuum drying, namely obtain catalyst GO/Fe
3o
4-CuI, with ICP-AES test, obtains Cu in catalyst
+load capacity be 11wt%.
By above-mentioned obtained catalyst GO/Fe
3o
4-CuI is used for the fluoro-2-iodobenzamide of catalysis 4-and leucine synthesis quianzolinones, and concrete steps are:
A () is by 0.018gGO/Fe
3o
4the fluoro-2-iodobenzamide of-CuI, 2.5mmol leucine, 2.5mmol cesium carbonate, 1mmol4-and 15ml ethylene glycol/methyl-sulfoxide add in round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 6h at 130 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of the quianzolinones of synthesis is 90%.
Embodiment 17
A kind of can the GO/Fe of magnetic recovery
3o
4-CuI catalyst, Cu
+load capacity be 10.5wt%, its preparation method comprises the following steps:
(1) graphene oxide powder is joined 2-Pyrrolidone, wherein, graphene oxide is 1g:300mL with the ratio of the addition of 2-Pyrrolidone, and ultrasonic process 3.5h obtains mixture in a nitrogen atmosphere;
(2) add hot mixt to 192 DEG C, and drip the praseodynium ferrous solution that concentration is 0.2mol/L under mechanical stirring, make Fe
3+compare for 20mmol:1g with the molal weight of graphene oxide, stirring and refluxing reaction 11h, obtains black precipitate GO/Fe
3o
4;
(3) by black precipitate GO/Fe
3o
4magnetic recovery, with absolute ethanol washing repeatedly, after 46 DEG C of vacuum drying, obtain GO/Fe
3o
4product;
(4) by GO/Fe
3o
4product and CuI add in absolute ethyl alcohol with mass ratio 2:1, in a nitrogen atmosphere, in 82 DEG C of magnetic stirring and refluxing 8.5h, by magnetic recovery black solid, then with absolute ethanol washing repeatedly, after 45 DEG C of vacuum drying, namely obtain catalyst GO/Fe
3o
4-CuI, with ICP-AES test, obtains Cu in catalyst
+load capacity be 10.5wt%.
By above-mentioned obtained catalyst GO/Fe
3o
4-CuI is used for the fluoro-2-iodobenzamide of catalysis 4-and leucine synthesis quianzolinones, and concrete steps are:
A () is by 0.02gGO/Fe
3o
4the fluoro-2-iodobenzamide of-CuI, 2.7mmol leucine, 3mmol cesium carbonate, 1mmol4-and 11ml ethylene glycol/methyl-sulfoxide add in round-bottomed flask, in ethylene glycol/methyl-sulfoxide, the volume ratio of ethylene glycol and methyl-sulfoxide is 1:60, mix and blend back flow reaction 6h at 122 DEG C;
B reacted mixed solution magnetic recovery is obtained black solid by (), then after washing drying, the GO/Fe be recycled
3o
4-CuI catalyst;
C residual mixed liquor ethyl acetate/water (volume ratio is 1:1) after magnetic recovery in step (b) extracts by (), organic phase pillar layer separation obtains quianzolinones, and its structural formula is:
The productive rate of the quianzolinones of synthesis is 87%.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. one kind can the GO/Fe of magnetic recovery
3o
4-CuI catalyst, is characterized in that, this catalyst is CuI doped F e
3o
4back loading on graphene oxide, wherein Cu
+load capacity be 10wt% ~ 11wt%.
2. one kind as claimed in claim 1 can the GO/Fe of magnetic recovery
3o
4the preparation method of-CuI catalyst, is characterized in that, the method comprises the following steps:
(1) graphene oxide powder is joined 2-Pyrrolidone, ultrasonic process 2 ~ 4h obtains mixture in a nitrogen atmosphere;
(2) add hot mixt, and drip praseodynium ferrous solution under mechanical stirring, stirring and refluxing, reaction, obtains black precipitate GO/Fe
3o
4;
(3) by black precipitate GO/Fe
3o
4after magnetic recovery, washing, drying, obtain GO/Fe
3o
4product;
(4) by GO/Fe
3o
4product and CuI add in absolute ethyl alcohol, magnetic stirring backflow in a nitrogen atmosphere, by magnetic recovery black solid, then wash, after drying, namely obtain catalyst GO/Fe
3o
4-CuI.
3. according to claim 2 a kind of can the GO/Fe of magnetic recovery
3o
4the preparation method of-CuI catalyst, is characterized in that, the mass volume ratio of the graphene oxide described in step (1) and 2-Pyrrolidone is (1 ~ 2) g:300mL.
4. according to claim 2 a kind of can the GO/Fe of magnetic recovery
3o
4the preparation method of-CuI catalyst, is characterized in that, the praseodynium ferrous solution described in step (2) is the solution of praseodynium dissolved ferric iron in 2-Pyrrolidone, and its concentration is 0.06 ~ 0.2mol/L; Fe
3+compare for 20mmol:1g with the molal weight of graphene oxide;
Praseodynium ferrous solution and graphene oxide reaction temperature be 185 ~ 195 DEG C, the reaction time is 8 ~ 12h.
5. according to claim 1 a kind of can the GO/Fe of magnetic recovery
3o
4the preparation method of-CuI catalyst, is characterized in that, the GO/Fe described in step (4)
3o
4be 2:1 with the addition mass ratio of CuI, reaction temperature is 75 ~ 85 DEG C, and the reaction time is 8 ~ 10h;
Step (3) and the washing described in step (4) are for adopting absolute ethanol washing repeatedly, and drying is vacuum drying at 40 ~ 50 DEG C.
6. one kind as claimed in claim 1 can the GO/Fe of magnetic recovery
3o
4the application of-CuI catalyst on synthesis quianzolinones, is characterized in that, comprise the following steps:
A () is by GO/Fe
3o
4-CuI, amino acid, cesium carbonate, adjacent halogen benzoyl amine and ethylene glycol/methyl-sulfoxide, at 110 ~ 130 DEG C, mix and blend backflow 5 ~ 7h;
B reacted mixed solution magnetic recovery is obtained black solid by (), after washing drying, and the GO/Fe be recycled
3o
4-CuI catalyst;
C the ethyl acetate of residual mixed liquor volume ratio 1:1 after magnetic recovery in step (b) and the extractant of water extract by (), be separated organic phase pillar layer separation and obtain quianzolinones.
7. according to claim 6 can the GO/Fe of magnetic recovery
3o
4the application of-CuI catalyst on synthesis quianzolinones, it is characterized in that, in step (a), the structural formula of described adjacent halogen benzoyl amine is as follows:
Wherein, R
1be selected from H, F or CH
3in one, R
2for H or F;
Described amino acid whose structural formula is as follows:
Wherein, R
3be selected from CH
2cH
2cH
3, CH (CH
3)
2, CH
2cH (CH
3)
2, CH
2(Ph) one or in Ph.
8. according to claim 6 can the GO/Fe of magnetic recovery
3o
4the application of-CuI catalyst on synthesis quianzolinones, it is characterized in that, adjacent halogen benzoyl amine described in step (a), the mol ratio of amino acid, cesium carbonate is 1:(2 ~ 3): (2 ~ 3), described ethylene glycol/methyl-sulfoxide is the ethylene glycol of volume ratio 1:60 and the mixture of methyl-sulfoxide, and its consumption is according to the interpolation 10 ~ 15mL of the adjacent halogen benzoyl amine of every 1mmol; Described GO/Fe
3o
4the consumption of-CuI is according to the interpolation 0.0150g ~ 0.0200g of the adjacent halogen benzoyl amine of every 1mmol.
9. according to claim 6 or 8 can the GO/Fe of magnetic recovery
3o
4the application of-CuI catalyst on synthesis quianzolinones, it is characterized in that, adjacent halogen benzoyl amine described in step (a), the mol ratio of amino acid, cesium carbonate is 1:3:3, and the consumption of ethylene glycol/methyl-sulfoxide is according to the interpolation 10mL of the adjacent halogen benzoyl amine of every 1mmol; Described GO/Fe
3o
4the consumption of-CuI is according to the interpolation 0.0200g of the adjacent halogen benzoyl amine of every 1mmol.
10. according to claim 6 can the GO/Fe of magnetic recovery
3o
4the application of-CuI catalyst on synthesis quianzolinones, is characterized in that, the drying of washing described in step (b) is with absolute ethyl alcohol and washs for several times, and 45 DEG C of vacuum drying are reclaimed.
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CN105858711A (en) * | 2016-03-30 | 2016-08-17 | 淮北师范大学 | Preparation method of CuI-graphene oxide nanocomposite |
CN105825990B (en) * | 2016-03-30 | 2017-11-14 | 淮北师范大学 | A kind of CuI Fe3O4The preparation method of magnetic nanocomposites |
CN105858711B (en) * | 2016-03-30 | 2018-03-13 | 淮北师范大学 | A kind of preparation method of CuI stannic oxide/graphene nano composites |
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CN114409684A (en) * | 2022-02-11 | 2022-04-29 | 合肥工业大学 | Preparation and application of chiral amino zinc alkoxide complex |
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