CN103467500B - A kind of copper complex - Google Patents
A kind of copper complex Download PDFInfo
- Publication number
- CN103467500B CN103467500B CN201310429053.0A CN201310429053A CN103467500B CN 103467500 B CN103467500 B CN 103467500B CN 201310429053 A CN201310429053 A CN 201310429053A CN 103467500 B CN103467500 B CN 103467500B
- Authority
- CN
- China
- Prior art keywords
- reaction
- title complex
- crystal
- synthesis
- thf
- 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
Landscapes
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
A preparation for copper compound, its chemical formula is as follows:
Description
One, technical field
The present invention relates to a kind of new compound and preparation method thereof, particularly a kind of copper compound and preparation method thereof, is exactly a kind of generation and synthesis method of adjacent cyanopyridine venus crystals title complex.
Two, background technology
Along with vitochemical development, the application of organometallics in organic synthesis is more and more wide, is one of field of very enlivening in present organic chemistry, has been widely used in organic synthesis.The asymmetric catalysis synthesis of the use chiral ligand that the later stage sixties 20th century occurs and transition metal complex catalysis accelerates the research of chiral drug greatly.The important content of chemical catalysis dissymmetric synthesis is the design of part and containing metal catalyzer, thus makes reaction have efficient and high enantioselectivity.
1, the metal complex catalyzed Asymmetric cyclopropanation of Shou bisoxazoline part one
The asymmetric cyclopropane of catalysis, than reaction, namely utilizes the cycloaddition reaction of the metal complex catalyzed diazonium compound of chiral ligand one and alkene, is the important means of synthesis photolytic activity cyclopropane moiety compound.Nineteen ninety, Masmune etc. utilize hand bisoxazoline part-copper complex catalysis cyclopropanization reaction respectively, all obtain very high enantioselectivity.
2, chiral copper catalyst one catalyzed alkene generation Asymmetric cyclopropanation reaction
The chiral copper catalyst catalyzed alkene generation Asymmetric cyclopropanation reaction of SUMITOMO CHEMICAL company, has synthesized dipeptide inhibitors Cilastatin.
Reference:
[1]Holmes F，Jones K M，et al.Complex-forming agents similar to2，2’bipyridyl.Part I.Someligands comaining imidazole.J Chem Soc，1961，4790-4794
[2] Fan Zhi, Wen Xin, Zhou Weihong, Liu little Lan, Miao Fangming. the synthesis of three (2-benzoglyoxaline methylene radical) amine copper (II) title complex, crystalline structure and quantum Chemical Study. Chinese Journal of Inorganic Chemistry, in September, 1999, the 5th phase: 602-606
[3] Tan Jun. the coordination chemistry research of quercetin with Cu (II) title complex. Chongqing Education College's journal, in November, 2006, the 19th volume the 6th phase: 11-15
[4] Li Qinling. the application of transition metal complex in chiral drug synthesis. Qinghai science and technology, the 1st phase: 45-49 in 2007
Three, summary of the invention
The present invention aims to provide adjacent cyanopyridine copper complex, and technical problem to be solved is that one-step synthesis obtains target product.
Title complex alleged by the present invention be by adjacent cyanopyridine and copper acetate dihydrate prepare by the compound shown in following chemical formula:
Chemical name: adjacent cyanopyridine venus crystals title complex, is called for short title complex (I).This title complex shows certain catalytic performance in the Henle reaction of 2-bromobenzaldehyde, and its transformation efficiency reaches 54.5%.
This synthetic method comprises synthesis and is separated, described synthesis takes 3.1233g (0.03mol) adjacent cyanopyridine and 1.9972g (0.01mol) hydration neutralized verdigris puts into 100ml round-bottomed flask, do reaction solvent adding 30ml tetrahydrofuran (THF), reflux stirs 48h.Heat filtering immediately after reaction terminates, to be spin-dried for after partially liq with preservative film sealing, to leave standstill, occur sapphire crystal after one day under normal temperature.
Building-up reactions is as follows:
This synthetic method one step obtains target product, and technique is simple, easy to operate.
Four, accompanying drawing explanation
Fig. 1 is the single X-ray diffractometer figure of adjacent cyanopyridine venus crystals title complex.
Five, embodiment
The preparation of adjacent cyanopyridine venus crystals title complex: take 3.1233g (0.03mol) adjacent cyanopyridine and 1.9972g (0.01mol) hydration neutralized verdigris puts into 100ml round-bottomed flask, do reaction solvent adding 30ml tetrahydrofuran (THF), reflux stirs 48h.Heat filtering immediately after reaction terminates, to be spin-dried for after partially liq with preservative film sealing, to leave standstill, occur sapphire crystal after one day under normal temperature.Elemental analysis data is as follows: theoretical value is C:42.03%; H:3.53%; N:9.80%.Measured value C:41.64%; H:3.53%; N:9.36%; The crystal data of 3500,3100,2250,1630,1400,1100,800,700. compounds:
The typical bond distance's data of crystal:
The typical bond angle data of crystal
。
(3), Henle reaction application
2-nitro-1-phenylethyl alcohol
Get the title complex I (catalytic amount is 15mol%) of 0.15mmol in the little flask of 25mL, add the absolute methanol solution of 2 milliliters, then, the 2-bromobenzaldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL is added in above-mentioned solution, stirring at normal temperature, react after 4 hours, carry out nmr analysis, transformation efficiency: 54.5%;
1hNMR (500MHz, CDCl
3) 7.65 (d, J=8z, 1H, Ar-H), 7.18 ~ 7.36 (m ,=8Hz, 3H, Ar-H), 4.88 ~ 4.90 (m, 2H), 4.82 ~ 4.84 (m, 1H).
Claims (3)
1. a copper complex, its chemical formula is as follows:
2. title complex according to claim 1 (I), at 140 (2) k temperature, on the X-ray single crystal diffraction instrument of Oxford, with the MoK alpha-ray through graphite monochromator monochromatization
collect diffraction data with ω-θ scan mode, it is characterized in that crystal belongs to rhombic system, spacer P2 (1) c,
α=90 °;
β=118.83 °;
γ=90 °.
3. the synthetic method of title complex according to claim 1 (I), comprise synthesis and be separated, it is characterized in that described synthesis takes the adjacent cyanopyridine of 3.1233g and 1.9972g mono-hydration neutralized verdigris puts into 100ml round-bottomed flask, 30ml tetrahydrofuran (THF) does reaction solvent, reflux stirs 48h, and heat filtering immediately after reaction terminates, seals with preservative film after being spin-dried for partially liq, leave standstill under normal temperature, after one day, occur sapphire crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310429053.0A CN103467500B (en) | 2013-09-09 | 2013-09-09 | A kind of copper complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310429053.0A CN103467500B (en) | 2013-09-09 | 2013-09-09 | A kind of copper complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103467500A CN103467500A (en) | 2013-12-25 |
| CN103467500B true CN103467500B (en) | 2015-09-30 |
Family
ID=49792570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310429053.0A Expired - Fee Related CN103467500B (en) | 2013-09-09 | 2013-09-09 | A kind of copper complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467500B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175453B (en) * | 2015-10-12 | 2017-09-26 | 合肥工业大学 | A kind of manganese complex is prepared and its synthetic method |
| CN105712927B (en) * | 2016-01-21 | 2017-12-01 | 合肥工业大学 | A kind of cobalt complex prepares and its synthetic method |
| CN106117250B (en) * | 2016-06-29 | 2018-01-26 | 合肥祥晨化工有限公司 | A kind of copper complex |
| CN106083902B (en) * | 2016-07-01 | 2018-01-26 | 合肥工业大学 | A kind of copper complex |
| CN108795417A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex yellow green phosphor material of chain structure |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696218B (en) * | 2009-10-30 | 2011-06-08 | 合肥工业大学 | Method for preparing o-aminopyridine copper coordination compound |
| CN101787042B (en) * | 2010-03-17 | 2012-01-18 | 合肥工业大学 | Copper-nitrogen compound and application thereof |
| CN102702236B (en) * | 2012-05-31 | 2015-03-25 | 合肥工业大学 | Copper nitrogen complex and application thereof |
-
2013
- 2013-09-09 CN CN201310429053.0A patent/CN103467500B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103467500A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467500B (en) | A kind of copper complex | |
| CN106582710B (en) | A kind of method that graphene-supported palladium copper nano-catalytic Suzuki reaction prepares biphenyl | |
| CN102807577B (en) | Chiral compound | |
| CN103588821B (en) | Chiral phenylglycinol nickel complex | |
| Kishore et al. | Ruthenium (II)-catalysed direct synthesis of ketazines using secondary alcohols | |
| CN102070673B (en) | O-amino benzylamine nickel coordination compound | |
| CN103570768B (en) | A kind of cobalt nitrogen complex | |
| CN103467313B (en) | Chiral copper complex | |
| CN107337652A (en) | A kind of Chiral oxazoline cobalt complex and purposes | |
| CN103275108B (en) | Preparation and synthesis method of chiral copper complex | |
| CN103464207A (en) | Rare-earth complex catalyst, and preparation method, application and application method thereof | |
| CN103613507B (en) | Chiral D-Phenylglycinol cobalt complex | |
| CN103570751A (en) | Chiral leucinol copper complex | |
| CN102850383B (en) | A kind of chiral zinc nitrogen complexes | |
| CN103641787A (en) | Chiral oxazolinyl cobalt complex and synthesis method thereof | |
| CN103804429B (en) | A kind of chirality leucinol cobalt complex | |
| CN108101755A (en) | A kind of method for preparing chiral 4- (2- propargyls) phenol compound | |
| CN103570562A (en) | Chiral Ni complex | |
| CN103664826B (en) | A kind of preparation method of aminonaphthol compound | |
| CN103304586B (en) | Chiral copper compound | |
| CN103073467A (en) | Preparation method of alpha-carbonyl sulfur ylide derivative | |
| CN103467311B (en) | Chiral cobalt complex | |
| CN103709047A (en) | Chiral (R)-phenylethylamine hydrochloride copper chloride complex | |
| CN105085578A (en) | Platinum complex crystal | |
| CN103724212A (en) | Chiral (S)-phenylethylamine hydrochloride cobalt chloride complex crystal |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150930 Termination date: 20180909 |