CN103570562A

CN103570562A - Chiral Ni complex

Info

Publication number: CN103570562A
Application number: CN201310570708.6A
Authority: CN
Inventors: 罗梅; 黄永华
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-11-17
Filing date: 2013-11-17
Publication date: 2014-02-12

Abstract

The chemical formula of a chiral Ni complex is shown in the specification. The synthetic method of the chiral Ni complex comprises the following steps: weighing 4.1162 g (0.03 mol) L- phenylglycinol, placing L- phenylglycinol into a 100 ml round-bottom flask, adding 50 ml absolute methanol, stirring to dissolve the L- phenylglycinol, adding 2.4892 g (0.01 mol) Ni (OAc) 2.4H2O in the solution, heating and refluxing for 48 h, filtering the reaction solution in heating, preparing a saturated solution with absolute ethyl alcohol after the spin-drying the filtrate is finished, standing for natural volatilization, and separating out blue crystals. The complex shows favorable catalytic performance in the Henry reaction of benzaldehyde, and the conversion rate of the complex reaches 54.3%.

Description

A kind of Chiral Nickel title complex

One, technical field

The present invention relates to a kind of new compound and preparation method thereof, particularly a kind of nickel compound and preparation method thereof, is exactly a kind of preparation and synthetic method of chirality L-benzene glycinol nickel complex.

Two, background technology

Chiral amino alcohol nickel complex is important catalyzer and medication chemistry product, and it has good catalytic effect as catalyzer in zinc ethyl reacts with phenyl aldehyde enantioselective addition etc.【1-6】

Reference:

1.Asymmetric hydrogenation catalyzed by bis(dimethylglyoximato)cobalt(II)-achiral base complex and chiral amino alcohol conjugated systems. Oxidoreductase model with enantioselectivity ，Ohgo, Yoshiaki; Natori, Yukikazu; Takeuchi, Seiji; Yoshimura, Juji , Chemistry Letters (1974), (11), 1327-30.

Synthesis, structure and acid-base properties of cobalt(III) complexes with aminoalcohols tepanenko, O. N.; Reiter, L. G. Ukrainskii Khimicheskii Zhurnal (Russian Edition), (1992), 58(12), 1047-54.

3. Cobalt(III) mono- and trinuclear complexes with O,N-chelating aminoalcohols apanadze, T. Sh.; Gulya, A. P.; Novotortsev, V. M.; Ellert, O. G.; Shcherbakov, V. M.; Kokunov, Yu. V.; Bushaev, Yu. A. Koordinatsionnaya Khimiya (1991), 17(7), 934-40.

4. Magnetic properties of cobalt complexes with amino alcohols, Evreev, V. N.; Bogdanov, A. P. 13 Vses. Chugaev. Soveshch. po Khimii Kompleks. Soedin., 1978 (1978), 137.

5.Synthesis, stereochemistry, and reactions of cobalt(III) complexes with amino alcohol ligands

Okamoto, Martha S. No Corporate Source data available | (1974), 146 pp.

6.Synthesis and properties of isomeric tris(N-[2-hydroxyethyl]ethylenediamine)cobalt(III) and tris(N-[2-hydroxypropyl]ethylenediamine)cobalt(III) chlorides, arpeiskaya, E. I.; Kukushkin, Yu. N.; Trofimov, V. A.; Yakovlev, I. P. , Zhurnal Neorganicheskoi Khimii (1971), 16(7), 1960-4。

Three, summary of the invention

The present invention aims to provide chirality three [(S)-benzene glycinol] nickelous acetate title complex.Technical problem to be solved is that one-step synthesis obtains target product.

The alleged chirality cobalt complex of the present invention be by nickel acetate tetrahydrate and L-benzene glycinol, prepared by the compound shown in following chemical formula:

(I)。

Chemical name: three [(S)-benzene glycinol] nickel complex, is called for short title complex (I).This title complex has shown certain catalytic performance in the Henle reaction of phenyl aldehyde, and its transformation efficiency reaches 54.3%.

This synthetic method comprises synthetic with separated, it is characterized in that: take 4.1162g (0.03mol) L-benzene glycinol and put into 100ml round-bottomed flask, add 50ml anhydrous methanol, stir it is dissolved, by 2.4892g (0.01mol) Ni (OAc) ₂4H ₂o adds above-mentioned solution, reflux 48h, and filtered while hot reaction soln, is spin-dried for after filtrate, with dehydrated alcohol, is mixed with saturated solution, and standing volatilization naturally, separates out blue colored crystal.

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 chirality three [(S)-benzene glycinol] nickel complex.

Five, embodiment

The preparation of chirality three [(S)-benzene glycinol] nickel complex:

Take 4.1162g (0.03mol) L-benzene glycinol and put into 100ml round-bottomed flask, add 50ml anhydrous methanol, stir it is dissolved, by 2.4892g (0.01mol) Ni (OAc) ₂4H ₂o adds above-mentioned solution, reflux 48h, and filtered while hot reaction soln, is spin-dried for after filtrate, with dehydrated alcohol, is mixed with saturated solution, and standing volatilization naturally, separates out blue colored crystal.Ultimate analysis C ₂₄h ₃₁ni ₃n ₃o ₃: theoretical value (%): C:61.57%; H:6.67%; N:8.97%; Measured value (%): C:61.48 %; H:7.01%; N:8.52 %54.38%; H:5.82%; N:7.49%; Productive rate is 78%; Fusing point is 85-87 ℃, [a] ⁵ _d=-148.81o (c 0.0484, CH3OH), and IR(KBr compressing tablet, cm ^-1): 3321,3276,3151,3064,2823,1552,1498,1461,1406,1341,1146,1028,914,833,760,700,654,541;

The crystal data of title complex (I):

Empirical formula C24H31N63O3Ni

Molecular weight 468.23

Temperature 293 (2) K

Wavelength 0.71073 A

Crystallographic system, spacer oblique system, P2 (1)

Unit cell parameters a=5.2581 (12) A alpha=90deg.

b = 23.683 (5) A beta = 97.93(6) deg.

c = 13.744(3) A gamma = 90deg.

Volume 1695.1(7) A^3

Electric density 2,0.917Mg/m^3

Absorption correction parameter 0.592 mm^-1

Number of electrons 496 in unit cell

Crystallographic dimension 0.212x 0.158x 0.117 mm

Scope 1.72 to 25.49 at Theta angle

Index capture range-6<=h<=6 of HKL ,-28<=k<24,0<=l<=16

Collection/independent diffraction data 5315/ 5315 [R (int)=0.0000]

Data integrity degree 99.9 % of theta=30.5

The method Multi Slice Mode of absorption correction

The Matrix least square method of the method F^2 that refine is used

Number/the number of parameters 5315/182/248 of data number/use restriction

The consistence factor R 1=0.0897 of point diffraction, wR2=0.2065

The identical factor R 1=0.10709 of observable diffraction, wR2=0.2162

Absolute configuration parameter 0.09(3)

Maximum summit on difference Fourier figure and peak valley 1.679 and-0.515e.A^-3

the typical bond distance's data of crystal:

Ni(1)-N(1) 2.054(7)

Ni(1)-N(2) 2.077(5)

Ni(1)-O(2) 2.090(5)

Ni(1)-N(3) 2.091(7)

Ni(1)-O(3) 2.117(5)

Ni(1)-O(1) 2.127(4)

O(1)-C(1) 1.396(9)

O(1)-H(1) 0.812(19)

O(2)-C(9) 1.398(10)

Claims

1. a Chiral Nickel title complex, its chemical formula is as follows:

（I）。

2. title complex claimed in claim 1 (I), at 293(2) at k temperature, on Oxford X-ray single crystal diffractometer, with the MoKa ray through graphite monochromator monochromatization (λ=0.71073 A), with w-Theta scan mode, collect diffraction data, it is characterized in that crystal belongs to rhombic system, spacer P2 (1), a=5.2581 (12) A alpha=90deg; B=23.683 (5) A, beta=97.93 (6) deg; C=13.744 (3) A gamma=90deg.

3. the synthetic method of title complex claimed in claim 1 (I), this synthetic method comprises synthetic with separated, it is characterized in that: take 4.1162g (0.03mol) L-benzene glycinol and put into 100ml round-bottomed flask, add 50ml anhydrous methanol, stirring is dissolved it, by 2.4892g (0.01mol) Ni (OAc) ₂4H ₂o adds above-mentioned solution, reflux 48h, and filtered while hot reaction soln, is spin-dried for after filtrate, with dehydrated alcohol, is mixed with saturated solution, and standing volatilization naturally, separates out blue colored crystal.