CN101327449B - Ion liquid carried Salen metallic catalyst and preparation method - Google Patents
Ion liquid carried Salen metallic catalyst and preparation method Download PDFInfo
- Publication number
- CN101327449B CN101327449B CN2008100630049A CN200810063004A CN101327449B CN 101327449 B CN101327449 B CN 101327449B CN 2008100630049 A CN2008100630049 A CN 2008100630049A CN 200810063004 A CN200810063004 A CN 200810063004A CN 101327449 B CN101327449 B CN 101327449B
- Authority
- CN
- China
- Prior art keywords
- ion liquid
- salen
- metallic catalyst
- liquid supported
- ion
- 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.)
- Expired - Fee Related
Links
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 title claims description 37
- 239000003863 metallic catalyst Substances 0.000 title claims description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000001455 metallic ions Chemical class 0.000 claims description 2
- 230000010148 water-pollination Effects 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 5
- 238000007306 functionalization reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 abstract 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- -1 triethylamine hexafluorophosphate Chemical compound 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 6
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 3
- 150000004753 Schiff bases Chemical class 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XEJHZDZOTCPPCM-UHFFFAOYSA-N [N+](=O)(O)[O-].CC=1NC=CN1 Chemical compound [N+](=O)(O)[O-].CC=1NC=CN1 XEJHZDZOTCPPCM-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XDKUKGIJDNUFGK-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CN=C[N]1 XDKUKGIJDNUFGK-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a Salen metal catalyst supported by ionic liquid and a preparation method thereof. Alkyl is used for substituting functionalization ionic liquid with side chain containing minus NH2 group to be reacted with substituted salicylaldehyde to obtain salicylaldehyde ligand supported by the ionic liquid; the salicylaldehyde ligand supported by the ionic liquid is reactedwith metal salt containing metal ion Cr<3 plus> or Co<3 plus> to obtain the Salen metal catalyst supported by the ionic liquid. The catalyst is simple for preparing, is stable in water and air and also has good thermal stability at the same time.
Description
Technical field
The present invention relates to the synthetic method of a class Salen metallic catalyst, particularly relate to ion liquid supported Salen metallic catalyst of a class and preparation method thereof.
Background technology
As everyone knows, be that the Salen catalyst in activated centre is at carbon dioxide copolymerization reaction (Acc.Chem.Res., 2004,37,836-844 with the metal; J.Am.Chem.Soc., 2005,127,14026-14038), oxidation reaction (US4970347, US4046813, CN1425642) etc. use very extensive in the course of reaction, but under most of situation, Salen metal species catalyst also has its intrinsic shortcoming, with Salen metal species catalyst carbon dioxide and epoxide copolyreaction is example, although Salen metal species catalyst has overcome organic zinc class catalyst (J.Polym.Sci.Part B:Polym.Let., 1969,7,287-292, with terres rares catalyst (CN 85104956) to problems such as water and air sensitivities, but existing Salen metallic catalyst catalytic efficiency is not high, reaction time is longer, the polycarbonate-based material molecule amount for preparing is less, and these problems have seriously limited its industrial applications.Therefore, development of new high efficiency, Salen metallic catalyst easy to operate, cheap and easy to get are the research directions of present carbon dioxide copolymerization catalyst.
Summary of the invention
The purpose of this invention is to provide novel ion liquid supported Salen metallic catalyst of a class and preparation method thereof, especially, the ion liquid supported Salen metallic catalyst of this class can change its solubility property in water and other organic solvents by the anion that changes combination with it.Such ion liquid supported Salen metallic catalyst preparation is simple relatively, and heat endurance is preferably arranged simultaneously.
The invention provides ion liquid supported Salen metallic catalyst, its structural formula is as follows:
In the formula: R
1, R
2, R
3, R
4, R
5Be H, Me, Et, Pr or Bu; The metal M ion is Co
3+Or Cr
3+Anion Y
-Be BF
4 -, PF
6 -, Cl
-, Br
-, F
-, PO
4 3-, SO
4 2-, NO
3 -, CH
3COO
-In a kind of.
The preparation method who the invention provides ion liquid supported Salen metallic catalyst is to replace side chain with alkyl and contain-NH
2Group functionalization's ionic liquid and substituted salicylic aldehydes reaction prepare ion liquid supported SalenH
2Part (a); SalenH
2Part again with metal ion Cr
3+Or Co
3+Reacting metal salt, prepare ion liquid supported Salen metallic catalyst (b); Reaction equation is as follows:
In the formula: R
1, R
2, R
3, R
4, R
5Be H, Me, Et, Pr, Bu etc., M is Co
3+Or Cr
3+Deng, Y
-Be BF
4 -, PF
6 -, Cl
-, Br
-, F
-, PO
4 3-, SO
4 2-, NO
3 -, CH
3COO
-Deng.
Be used for an ionic liquid that carries the Salen metallic catalyst among the present invention and can replace quaternary ammonium type for imidazole type, pyridine type and alkyl.
Alkyl replacement side chain contains-NH among the present invention
2Group functionalization's the ionic liquid and the mol ratio of substituted salicylic aldehydes are between 1: 10~10: 1.
SalenH among the present invention
2Part and metal ion Cr
3+Or Co
3+The mol ratio of slaine be between 1: 10~10: 1.
Intermediate ion liquid of the present invention props up the SalenH that carries
2Part (a) synthesis reaction temperature is between 0 ℃~200 ℃, and preferably between 5 ℃~80 ℃, the solvent that is suitable for this reaction is a methyl alcohol, ethanol, isopropyl alcohol, acetone, acetonitrile, chloroform etc.
Intermediate ion liquid of the present invention props up Salen metallic catalyst (b) synthesis reaction temperature that carries between 10 ℃~150 ℃, and preferably between 30 ℃~80 ℃, the solvent that is suitable for this reaction is a methyl alcohol, ethanol, and isopropyl alcohol etc., the Salen central metallic ions is Cr
3+Or Co
3+Deng.
Among the present invention, can change the solubility property of ion liquid supported Salen catalyst by the anion that changes supported ionic liquid.Work as Y
-Be PF
6 -During ion, the ion liquid supported catalysts for preparing is hydrophobic; Work as Y
-Be BF
4 -, Cl
-, Br
-, F
-, PO
4 3-, SO
4 2-, NO
3 -, CH
3COO
-During a kind of in the ion, the ion liquid supported catalysts for preparing is a hydrophily.
The specific embodiment
Following embodiment will more comprehensively describe the present invention.
Embodiment 1
A. the ion liquid supported schiff base ligand of triethylamine hexafluorophosphate is synthetic
Taking by weighing triethylamine 0.05mol (14.5g) is dissolved in and places the 500ml four-hole bottle that stirring arm, constant pressure funnel, reflux condensing tube and thermometer are housed, nitrogen protection in the 200ml methyl alcohol.The reflux condensing tube outlet inserts bubbler.Be dissolved in 0.05mol (5.4g) salicylide in the 80ml absolute ethyl alcohol and put into constant pressure funnel, under 75 ℃, drip 1h gradually, reflux and stir 4h.Slowly be cooled to below 5 ℃ and stir 1h.Vacuum filtration is used absolute ethanol washing 3-4 time, vacuum drying.Obtain the ion liquid supported schiff base ligand of triethylamine hexafluorophosphate (a), productive rate is more than 90%.
B. the ion liquid supported Salen metallic catalyst (b) of triethylamine hexafluorophosphate is synthetic
The schiff base ligand (a) that 4.7g (0.02mol) is ion liquid supported is dissolved in the 500ml four-hole round-bottomed flask of packing in the 200ml absolute ethyl alcohol.With 5.3g (0.0204mol) CrCl
36H2O is dissolved in the 100ml constant pressure funnel of packing in the 80ml absolute ethyl alcohol, inserts four-hole bottle, nitrogen protection, and 70 ℃ slowly drip 1h down.Dropwise the back and continue stirring and refluxing 4h.Decompression distillation obtains pressed powder after removing and desolvating, and puts into the vacuum drying oven drying, productive rate 85.6% after the acetone washing.
Embodiment 2
A. the ion liquid supported part of butyl-pyridinium four hexafluorophosphates is synthetic
Taking by weighing butyl-pyridinium four hexafluorophosphate ionic liquid 0.05mol (14.1g) is dissolved in and places the 500ml four-hole bottle that stirring arm, constant pressure funnel, reflux condensing tube and thermometer are housed, nitrogen protection in the 200ml methyl alcohol.The reflux condensing tube outlet inserts bubbler.Be dissolved in 0.05mol (5.4g) salicylide in the 80ml absolute ethyl alcohol and put into constant pressure funnel, under 75 ℃, drip 1h gradually, reflux and stir 4h.Slowly be cooled to below 5 ℃ and stir 1h.Vacuum filtration is used absolute ethanol washing 3-4 time, vacuum drying.Obtain the ion liquid supported Salen part (a) of butyl-pyridinium four hexafluorophosphates, productive rate is more than 90%.
B. the ion liquid supported Salen metallic catalyst (b) of butyl-pyridinium four hexafluorophosphates is synthetic
The part that 0.01mol is ion liquid supported is dissolved in the 500ml four-hole round-bottomed flask of packing in the 200ml absolute ethyl alcohol.0.0204mol CrCl36H2O is dissolved in the 100ml constant pressure funnel of packing in the 80ml absolute ethyl alcohol, inserts four-hole bottle, nitrogen protection, 75 ℃ slowly drip 1h down.Dropwise the back and continue stirring and refluxing 3h.Decompression distillation obtains pressed powder after removing and desolvating, and puts into the vacuum drying oven drying, productive rate 85.5% after the acetone washing.
Embodiment 3-6
Preparation method with reference to embodiment 1 step a contains-NH
2Group ionic liquid (a) obtains ion liquid supported SalenH with the substituted salicylic aldehydes reaction
2Synthetic reaction sees Table 1 under part (b) different solvents and the different temperatures
Embodiment | Ionic liquid (a) | Reaction dissolvent | Reaction temperature ℃ | Productive rate |
3 | Tripropyl amine (TPA) nitrate functional-type ionic liquid | Methyl alcohol | 55 | ?94% |
4 | Methylimidazole nitrate functional-type ionic liquid | Isopropyl alcohol | 150 | ?91% |
5 | Tripropyl amine (TPA) nitrate functional-type ionic liquid | Ethanol | 90 | ?93% |
6 | Pyridinium tetrafluoroborate salt functional-type ionic liquid | Chloroform | 70 | ?95% |
Embodiment 7-9
With reference to the preparation method of embodiment 1 step 3, SalenH
2Part (b) and reacting metal salt prepare that synthetic reaction sees Table 3 under ion liquid supported Salen metallic catalyst (c) different metal salt, solvent and the different temperatures
Embodiment | Ion liquid supported SalenH 2Part (b) | Slaine | Reaction dissolvent | Reaction temperature ℃ | Productive rate |
7 | The Salen part that tripropyl amine (TPA) nitrate functional-type is ion liquid supported | CrCl 3·6H 2O | Isopropyl alcohol | 30 | ?83.5% |
8 | The Salen part that methylimidazole nitrate functional-type is ion liquid supported | CrCl 3·6H 2O | Ethanol | 50 | ?89% |
Embodiment | Ion liquid supported SalenH 2Part (b) | Slaine | Reaction dissolvent | Reaction temperature ℃ | Productive rate |
9 | The Salen part that methylimidazole nitrate functional-type is ion liquid supported | Co(OAc) 2·4H 2O | Isopropyl alcohol | 80 | ?86% |
Claims (5)
2. according to the described ion liquid supported Salen metallic catalyst of claim 1, it is characterized in that: work as Y
-Be PF
6 -During ion, be the hydrophobicity catalyst; Work as Y
-Be BF
4 -, Cl
-, Br
-, F
-, PO
4 3-, SO
4 2-, NO
3 -, CH
3COO
-During a kind of in the ion, be the hydrophily catalyst.
3. the preparation method of the described ion liquid supported Salen metallic catalyst of claim 1 is characterized in that: replace side chain with alkyl and contain-NH
2The functionalized ionic liquid of group and substituted salicylic aldehydes reaction prepare ion liquid supported SalenH
2Part (a); SalenH
2Part (a) again with metal ion Cr
3+Or Co
3+Reacting metal salt, prepare ion liquid supported Salen metallic catalyst (b); Reaction equation is as follows:
In the formula: R
1, R
2, R
3, R
4, R
5Be H, Me, Et, Pr or Bu; Metal ions M is Co
3+Or Cr
3+, anion Y
-Be BF
4 -, PF
6 -, Cl
-, Br
-, F
-, PO
4 3-, SO
4 2-, NO
3 -Or CH
3COO
-
4. preparation method according to claim 3 is characterized in that: prepare ion liquid supported SalenH
2In part (a) reaction, organic solvent is a methyl alcohol, ethanol, and isopropyl alcohol, acetone, acetonitrile, a kind of in the chloroform, reaction temperature is between 10-150 ℃.
5. preparation method according to claim 3 is characterized in that: prepare in the reaction of ion liquid supported Salen metallic catalyst (b), organic solvent is a methyl alcohol, ethanol, and a kind of in the isopropyl alcohol, the Salen central metallic ions is Cr
3+Or Co
3+
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008100630049A CN101327449B (en) | 2008-07-10 | 2008-07-10 | Ion liquid carried Salen metallic catalyst and preparation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008100630049A CN101327449B (en) | 2008-07-10 | 2008-07-10 | Ion liquid carried Salen metallic catalyst and preparation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101327449A CN101327449A (en) | 2008-12-24 |
CN101327449B true CN101327449B (en) | 2010-06-16 |
Family
ID=40203592
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2008100630049A Expired - Fee Related CN101327449B (en) | 2008-07-10 | 2008-07-10 | Ion liquid carried Salen metallic catalyst and preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101327449B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101940947B (en) * | 2010-07-05 | 2011-12-21 | 沈阳化工大学 | Method for preparing polystyrene resin-immobilized Salon-Co (III) catalyst |
CN105949451B (en) * | 2016-07-14 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of method of alkali ionic liquid catalyzed preparation of poly carbonic ester |
CN106190216B (en) * | 2016-07-20 | 2017-12-22 | 昆明理工大学 | The technique that M (salen) is catalyzed paper catalytically liquefying biomass in a kind of ionic liquid |
-
2008
- 2008-07-10 CN CN2008100630049A patent/CN101327449B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN101327449A (en) | 2008-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107827855A (en) | The method for preparing cyclic carbonate ester | |
CN109331872B (en) | Application of n-butyl lithium in catalyzing imine and borane hydroboration reaction | |
Ulusoy et al. | Structural, spectral, electrochemical and catalytic reactivity studies of a series of N2O2 chelated palladium (II) complexes | |
CN101327452B (en) | Salen metallic catalyst and preparation method | |
CN101327449B (en) | Ion liquid carried Salen metallic catalyst and preparation method | |
CN106045913B (en) | A kind of imidazoles perrhenate ions liquid and its preparation method and application with amino | |
CN104277017B (en) | 2,5-dihydroxymethyl furans prepares the method for 2,5-dimethylin furans | |
CN114716371B (en) | N-containing active center metal organic catalyst for synthesizing cyclic carbonate, and preparation method and application thereof | |
CN106008401A (en) | Preparation method of N-formamide compound | |
CN110294689B (en) | Method for preparing nitrile compound by dehydrogenation of primary amine under catalysis of ruthenium metal complex | |
CN109012748B (en) | Pyridine substituted pyrrole based rare earth metal catalyst and preparation method and application thereof | |
CN101327450A (en) | Aminoacid ion liquid carried Salen metallic catalyst and preparation method | |
Kharat et al. | Green and chemoselective oxidation of alcohols with hydrogen peroxide: A comparative study on Co (II) and Co (III) activity toward oxidation of alcohols | |
CN102188998B (en) | Water oxidation catalyst containing ruthenium as well as preparation and application thereof | |
CN107935860B (en) | A method of preparing allylic amines compound | |
CN108273507B (en) | Method for reducing nitrile compound by catalytic hydrogenation | |
CN102304062B (en) | Method for preparing Salen Ni | |
CN102850153A (en) | Asymmetric reduction reaction method for catalyzing alpha, beta-unsaturated ketene and saturated ketene | |
ES2255569T3 (en) | PROCEDURE FOR THE ISOMERIZED OF ALILIC ALCOHOLS. | |
CN108623493B (en) | Under mild condition with CO2N-formylation synthesis method for carbon source | |
Gharah et al. | Synthesis and catalytic epoxidation potential of oxodiperoxo molybdenum (VI) complexes with 2-hydroxybenzohydroxamate and 2-hydroxybenzoate: the crystal structure of PPh 4 [MoO (O 2) 2 (HBA)] | |
CN109251217B (en) | Application of o-methoxyanilino lithium in catalysis of imine and borane hydroboration reaction | |
CN109289914B (en) | Application of o-methyl aniline lithium in catalyzing imine and borane hydroboration reaction | |
CN106905166B (en) | A method of synthesis secondary amine | |
CN105175297A (en) | Synthesis and application of 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100616 Termination date: 20120710 |