CN107814731A - A kind of Chiral Ni complex - Google Patents
A kind of Chiral Ni complex Download PDFInfo
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- CN107814731A CN107814731A CN201610818518.5A CN201610818518A CN107814731A CN 107814731 A CN107814731 A CN 107814731A CN 201610818518 A CN201610818518 A CN 201610818518A CN 107814731 A CN107814731 A CN 107814731A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
A kind of Chiral Ni complex（I）, its chemical formula is as follows：The synthetic method of the complex (I):Weigh 0.03mol（R）Valerian ammonia alcohol is put into 100mL round-bottomed flasks, adds 40ml absolute methanols, and stirring makes its dissolving；Weighing 0.01mol NiCl2·6H2O is added in above-mentioned solution, and control temperature is heated to reflux 36h at 75 DEG C or so；Filtering reacting solution while hot, solution is threaded to half solution with Rotary Evaporators, 5ml or so n-hexane is added in surplus solution, stood volatilization, after 2 weeks, there is blue colored crystal precipitation；Crystal is filtered out, crystal is rinsed 3 times with petroleum ether, is dried in vacuo 30 minutes, obtains target product;The compound benzaldehyde allyl group alkylated reaction, Baylis Hillman reaction and nitrile silicification reaction in show certain catalytic performance, its conversion ratio is respectively up to 76%, 78% and 66%.
Description
First, technical field
The present invention relates to a kind of noval chemical compound and preparation method thereof, more particularly to a kind of nickel compound and preparation method thereof, definitely
Ground say be a kind of chiral D-valerian ammonia alcohol nickel complex preparation and synthetic method.
2nd, background technology
Chiral amino alcohol nickel complex is important catalyst and medication chemistry product, and it is as catalyst in diethyl zinc and benzene
Preferable catalytic performance has been shown in the addition reaction of formaldehyde.【1】
Bibliography：
1. Catalytic enantioselective conjugate addition of diethylzinc to
chalcones using chiral amino alcohol-nickel complexes, Wakimoto, Izumi;
Tomioka, Yuko; Kawanami, Yasuhiro , Tetrahedron (2002), 58(40), 8095-8097。
3rd, the content of the invention
The present invention is intended to provide chirality three [（R）- valerian ammonia alcohol] chlorination nickel complex.Technical problem to be solved is that a step is closed
Into obtaining target product.
Chiral zinc nitrogen complexes alleged by the present invention are by below formula by Nickel dichloride hexahydrate with the preparation of D- valerian ammonia alcohols
Shown compound：
(I)。
Chemical name：Three [（R）- valerian ammonia alcohol] chlorination nickel complex, abbreviation complex (I).The compound is in benzaldehyde
Allyl group alkylated reaction, Baylis-Hillman reaction and nitrile silicification reaction in show certain catalytic performance, its convert
Rate reaches up to 76%, 78% and 66% respectively.
This synthetic method includes synthesis and separation, weighs 3.1420g (0.03mol) D- valerian ammonia alcohols and is put into 100mL round bottoms burning
In bottle, 40ml absolute methanols are added, stirring makes its dissolving；Weighing 2.4284g (0.01mol) NiCl2·6H2O adds above-mentioned molten
In liquid, control temperature is heated to reflux 36h at 75 DEG C or so；Filtering reacting solution while hot, solution is threaded to one with Rotary Evaporators
Half solution, 5ml or so n-hexane is added in surplus solution, stand volatilization.After 2 weeks, there is blue colored crystal precipitation.Filter out crystal,
Crystal is rinsed 3 times with petroleum ether, is dried in vacuo 30 minutes, obtains target product 2.1800g, yield：49%.Elementary analysis number
According to theoretical value (%)：C, 41.03; H, 8.95; N9.57;Measured value (%)：C, 41.48; H, 8.99; N, 9.73.
Synthetic reaction is as follows：
The step of this synthetic method one obtains target product, and technique is simple, easy to operate.
4th, illustrate
Fig. 1 be chirality three [（R）- valerian ammonia alcohol] chlorination nickel complex single X-ray diffractometer figure.
5th, embodiment
(1), chirality three [（R）- valerian ammonia alcohol] chlorination nickel complex preparation：
Weigh 3.1420g (0.03mol)（R）- valerian ammonia alcohol is put into 100mL round-bottomed flasks, adds 40ml absolute methanols, and stirring makes
It dissolves；Weighing 2.4284g (0.01mol) NiCl2·6H2O is added in above-mentioned solution, and control temperature is at 75 DEG C or so, heating
Flow back 36h；Filtering reacting solution while hot, solution is threaded to half solution with Rotary Evaporators, it is left that 5ml is added in surplus solution
Right n-hexane, stand volatilization.After 2 weeks, there is blue colored crystal precipitation.Crystal is filtered out, crystal is rinsed 3 times with 30~60 petroleum ethers,
Vacuum drying 30 minutes, obtains target product 2.1800g, yield：49%.Elemental analysis data, theoretical value (%)：C, 41.03;
H, 8.95; N9.57;Measured value (%)：C, 39.48; H, 8.99; N, 8.73;
The crystal data of compound：
Empirical formula C15H39N3O3NiCl2
Molecular weight 439.10
Temperature 100.01 (10) K
Wavelength 0.71073
Crystallographic system, Space group Monoclinic system, P2 (1) 2 (1) 2 (1)
Cell parameter a=15.7290 (9) α=90 °
b = 13.5454 (5) Å β = 90 °.
c = 11.5166 (4) Å γ = 90 °.
Volume 2453.68（4）
Charge density 4,1.189Mg/m^3
The mm^-1 of absorption correction parameter 1.024
Number of electrons 944 in unit cell
The mm of crystal size 0.25x 0.2x 0.05
The to 59.384 of scope 6.55 at Theta angles
HKL index capture range -14<=h<=21, -12<=k<18, -15<=l<=10
The % of data integrity degree 100.0 of theta=30.5
The method Multi Slice Mode of absorption correction
The Matrix least square method for the method F^2 that refine uses
Number/number of parameters 5523/3/233 of data number/use limitation
The method 1.019 that refine uses
The uniformity factor R 1=0.0471 of point diffraction, ω R2=0.0998
The identical factor R 1=0.0572 of observable diffraction, ω R2=0.1034
And -0.46e. the ^-3 of maximum summit and peak valley 0.87 on difference Fourier figure
The typical bond distance's data of crystal：
The typical bond angle data of crystal：
Nitrile silicification reaction application
2- phenyl -2-（Three silyloxies）Propionitrile
The ml (3.3mmol) of 0.1mmol complex I, benzaldehyde 0.1mL, TMSCN 0.3,2mL dichloromethane exist in succession
Added under 20 ~ 30 C, after 24 hours, add water quenching and go out after post layer（Petroleum ether/dichloromethane：5/1）, obtain colorless oil liquid
Body, yield are respectively：66%；1H NMR (300MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31–
7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8
(x2), 126.2(x2), 119.1, 63.5, -0.39(x3)；
Allyl group alkylated reaction application
Take 0.10mmol complex I（Catalytic amount is 10%）In 25mL small flask, it is molten to add 2 milliliters of dichloromethane
Liquid, then, 0.1mL benzaldehyde and 0.3mL allyl trimethyl silane, stirring at normal temperature, reaction are added into above-mentioned solution
After 48 hours, nmr analysis, conversion ratio are carried out：76%；1H NMR (300MHz, CDCl3) 7.27~7.33 (m, 5H, Ar-
), H 5.79~5.80 (m, 1H), 5.12~5.17 (m, 2H ,-CH2), 4.71（D, J=5Hz, 1H）, 2.49~2.50
(m, 2H), 2.28（s, 1H）；
Baylis-Hillman reactive applications
Take 0.10mmol complex I（Catalytic amount is 10%）In 25mL small flask, it is molten to add 2 milliliters of dichloromethane
Liquid, then, 0.1mL benzaldehyde and 0.5mL methyl acrylates are added into above-mentioned solution, stirring at normal temperature, is reacted small 72 hours
Afterwards, nmr analysis, conversion ratio are carried out：68%;1HNMR (300MHz, CDCl3) 7.20~7.41 (m, 5H, Ar-H),
6.30(s, 1H), 5.45 (s, 1H), 3.70(s, 3H), 3.15(s, 1H)。
Claims (3)
- A kind of 1. Chiral Ni complex（I）, its chemical formula is as follows：（I）.
- 2. the complex (I) described in claim 1, at a temperature of 100 K, on the X-ray single crystal diffractometer of Oxford, with through stone MoK alpha rays λ=0.71073 of black monochromator monochromatization, diffraction data is collected with ω-θ scan modes, it is characterised in that brilliant Body category orthorhombic system, space group anorthic system, P2 (1), cell parameter:A=15.7290 (9), α=90 °; b = 13.5454 (5) Å ,β = 90 °;C=11.5166 (4), γ=90 °.
- 3. the synthetic method of the complex (I) described in claim 1, including synthesize and separate, it is characterised in that described synthesis Weigh 0.03mol（R）- valerian ammonia alcohol is put into 100mL round-bottomed flasks, adds 40ml absolute methanols, and stirring makes its dissolving；Weighing 0.01molNiCl2·6H2O is added in above-mentioned solution, and control temperature is heated to reflux 36h at 75 DEG C or so；Filtering reaction while hot is molten Liquid, solution is threaded to half solution with Rotary Evaporators, 5ml or so n-hexane is added in surplus solution, stand volatilization；2 weeks Afterwards, there is blue colored crystal precipitation；Crystal is filtered out, crystal is rinsed 3 times with petroleum ether, is dried in vacuo 30 minutes, obtains target product.
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| CN201610818518.5A CN107814731A (en) | 2016-09-13 | 2016-09-13 | A kind of Chiral Ni complex |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450034A (en) * | 2013-09-22 | 2013-12-18 | 罗梅 | Chiral nickel complex |
| CN103570562A (en) * | 2013-11-17 | 2014-02-12 | 罗梅 | Chiral Ni complex |
| CN105111094A (en) * | 2015-09-06 | 2015-12-02 | 合肥祥晨化工有限公司 | Preparation and synthesis method of chiral nickel coordination compound crystal |
| CN105669772A (en) * | 2016-02-23 | 2016-06-15 | 合肥祥晨化工有限公司 | Preparation and synthesis method of nickel complex |
| CN105777562A (en) * | 2016-04-11 | 2016-07-20 | 合肥祥晨化工有限公司 | Chiral zinc complex crystal |
-
2016
- 2016-09-13 CN CN201610818518.5A patent/CN107814731A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450034A (en) * | 2013-09-22 | 2013-12-18 | 罗梅 | Chiral nickel complex |
| CN103570562A (en) * | 2013-11-17 | 2014-02-12 | 罗梅 | Chiral Ni complex |
| CN105111094A (en) * | 2015-09-06 | 2015-12-02 | 合肥祥晨化工有限公司 | Preparation and synthesis method of chiral nickel coordination compound crystal |
| CN105669772A (en) * | 2016-02-23 | 2016-06-15 | 合肥祥晨化工有限公司 | Preparation and synthesis method of nickel complex |
| CN105777562A (en) * | 2016-04-11 | 2016-07-20 | 合肥祥晨化工有限公司 | Chiral zinc complex crystal |
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Application publication date: 20180320 |