CN103923108A

CN103923108A - Copper complex and use

Info

Publication number: CN103923108A
Application number: CN201410181064.6A
Authority: CN
Inventors: 罗梅; 黄永华
Original assignee: Individual
Current assignee: Individual
Priority date: 2014-05-04
Filing date: 2014-05-04
Publication date: 2014-07-16

Abstract

The invention provides a copper complex shown by the following chemical formula in the specification. The synthesis method of the complex includes: measuring and putting 1.9120 g (0.01 mol) N-(2-hydroxyethyl) phthalimide in a 100 ml round bottom flask, adding 50 ml of absolute methanol, stirring to dissolve the N-(2-hydroxyethyl) phthalimide, adding 0.994 g (0.005 mol) Cu(OAc)2.H2O into the solution, heating for reflux for 48 hours, and thermally filtering the reaction solution, stewing to naturally volatilize to separate out blue crystals. The metal organic complex is used in a Henry reaction of benzaldehyde, and the conversion rate reaches 55.2%.

Description

A kind of copper complex and purposes

one, technical field

The present invention relates to the Preparation method and use of a kind of organometallic complex (title complex), the particularly Preparation method and use of nitrogenous a metal-organic complex, is exactly a kind of synthetic method and purposes of methanol acetic acid copper complex.

two, background technology

Along with vitochemical development, the application of organometallics in organic synthesis is more and more wide, is one of field very active in present organic chemistry, has been widely used in organic synthesis.The use chiral ligand that the later stage sixties 20th century occurs and the asymmetric catalysis synthesis of transition metal complex catalysis have accelerated the research of chiral drug greatly.The important content of chemical catalysis dissymmetric synthesis is the design of chiral ligand and containing metal catalyzer, thereby makes reaction have efficient and high enantioselectivity.The existing many bibliographical informations of synthetic method of methanol acetic acid copper complex, reference is as follows:

Reference:

1. Isotypic crystal structures of tetrakis(μ- acetato) bis(methanol) dicopper(II) and dirhodium(II)

Noinville, Vincent; Viossat, Bernard; Dung, Nguyen Huy , Acta Crystallographica, Section C: Crystal Structure Communications (1993), C49(7), 1297-8;

2. X- ray crystal structures of some adducts of dimeric copper(II) acetate. Nature of the copper- copper interaction, Rao, Vattipalli Mohan; Sathyanarayana, Dinit N.; Manohar, Hattikuolus , Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999) (1983), (10), 2167-73。

three, summary of the invention

The present invention aims to provide a kind of synthetic method of methanol acetic acid copper complex, and technical problem to be solved is one-step synthesis methanol acetic acid copper a metal-organic complex.

A kind of N-(2-hydroxyethyl) phthalimide of the alleged methanol acetic acid copper complex of the present invention and a hydration neutralized verdigris and methanol solvate prepare by the title complex shown in following chemical formula:

（Ⅰ）。

Chemical name: methanol acetic acid copper complex, is called for short title complex (I).

This synthetic method comprises synthesizes and separates, the described synthetic 1.9120g of measuring (0.01mol) N-(2-hydroxyethyl) phthalimide is put into 100ml round-bottomed flask, add 50ml anhydrous methanol, stirring is dissolved it, by 0.994g (0.005mol) Cu (OAc) ₂h ₂o adds above-mentioned solution, and after reflux 48h, heat filtering reaction soln, leaves standstill nature volatilization, 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.

Henry reaction is one of classical organic name reaction.This reaction refers to normally aromatic aldehyde and have the condensation reaction between the nitro-compound of α-hydrogen of carbonyl compound, and the result of reaction is that the alpha-carbon atom of nitro adds on carbonyl, forms the compound of the bifunctional with hydroxyl, nitro.The product of Henry reaction can be converted into the compound that has important use of all kinds easily, as beta-alkamine, nitroolefin, nitroketone, nitro ketenes or carry out Nef reaction.Therefore Henry reaction is one of very practical reaction in organic synthesis.Expand the range of application of this reaction, synthetic have a more more complicated compound in polyfunctional group, structure, is a significant job.

The alleged methanol acetic acid copper complex of the present invention has shown certain catalytic performance in the Henle reaction of phenyl aldehyde, and its transformation efficiency reaches 55.2%.

Four, brief description of the drawings

The X-diffraction analysis figure of Fig. 1 methanol acetic acid copper complex.

Five, embodiment

1. the preparation of methanol acetic acid copper complex

Measure 1.9120g (0.01mol) N-(2-hydroxyethyl) phthalimide and put into 100ml round-bottomed flask, add 50ml anhydrous methanol, stir it is dissolved, by 0.994g (0.005mol) Cu (OAc) ₂h ₂o adds above-mentioned solution, and after reflux 48h, filtered while hot reaction soln, leaves standstill nature volatilization, separates out blue colored crystal, productive rate: 52%; Fusing point: 140-146 DEG C, C ₁₀h ₂₀cu ₂o ₁₀theoretical value (%): C:56.21%; H:4.68%; Measured value (%): C:56.20 %; H:4.69; Infrared spectra number (KBr; V; Cm ^-1): 3473,2954,2887,1767,1697,1438,1396,1188,1132,1058,901,803,725,534;

Match crystal volume data is as follows:

Empirical formula C10H20O10Cu2

Molecular weight 427.34

Temperature 133 (2) K

Wavelength 0.71073 A

Crystallographic system, spacer oblique system, P2 (1)/n

Unit cell parameters a=7.9752 (14) A alpha=90deg.

b = 7.3926(13) A beta = 92.554(3) deg.

c = 13.192(2) A gamma = 90 deg.

Volume 777.0 (2) A^3

Electric density 2,1.827 Mg/m^3

Absorption correction parameter 2.783 mm^-1

Number of electrons 436 in unit cell

Crystallographic dimension 0.12x 0.06x 0.05 mm

Scope 2.93 to 30.57 at Theta angle

Index capture range-11<=h<=11 of HKL ,-8<=k<10 ,-18<=l<=18

Collection/independent diffraction data 7399/2370 [R (int)=0.0569]

Data integrity degree 99.4 % of theta=30.5

The method Multi Slice Mode of absorption correction

Transmitance 0.8734 and 0.7312 of minimax

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

Number/the number of parameters 2370/0/103 of data number/use restriction

The method 1.066 that refine is used

The consistence factor R 1=0.0396 of point diffraction, wR2=0.0956

The identical factor R 1=0.0587 of observable diffraction, wR2=0.1034

Maximum summit on difference Fourier figure and peak valley 0.862 and-0.766e.A^-3

the typical bond distance's data of crystal:

Cu(1)-O(2) 1.953(2)

Cu(1)-O(1)#1 1.960(2)

Cu(1)-O(5)#1 1.965(2)

Cu(1)-O(4) 1.976(2)

Cu(1)-O(3) 2.152(2)

Cu(1)-Cu(1)#1 2.5860(8)

O(1)-C(1) 1.266(4)

O(1)-Cu(1)#1 1.960(2)

O(2)-C(1) 1.266(4)

O(3)-C(3) 1.429(4)

O(3)-H(3D) 0.9500

O(4)-C(4) 1.272(4)

O(5)-C(4) 1.250(4)

O(5)-Cu(1)#1 1.965(2)

the typical bond angle data of crystal:

O(2)-Cu(1)-O(1)#1 169.97(9)

O(2)-Cu(1)-O(5)#1 90.24(9)

O(1)#1-Cu(1)-O(5)#1 89.84(9)

O(2)-Cu(1)-O(4) 89.03(9)

O(1)#1-Cu(1)-O(4) 89.12(9)

O(5)#1-Cu(1)-O(4) 169.78(9)

O(2)-Cu(1)-O(3) 93.13(9)

O(1)#1-Cu(1)-O(3) 96.84(9)

O(5)#1-Cu(1)-O(3) 95.68(9)

O(4)-Cu(1)-O(3) 94.54(9)

O(2)-Cu(1)-Cu(1)#1 85.84(7)

O(1)#1-Cu(1)-Cu(1)#1 84.19(6)

O(5)#1-Cu(1)-Cu(1)#1 83.84(6)

O(4)-Cu(1)-Cu(1)#1 85.94(6)

O(3)-Cu(1)-Cu(1)#1 178.86(6)

C(1)-O(1)-Cu(1)#1 123.18(19)

C(1)-O(2)-Cu(1) 121.67(19)

C(3)-O(3)-Cu(1) 119.98(18)

C(3)-O(3)-H(3D) 120.0

Cu(1)-O(3)-H(3D) 120.0

C(4)-O(4)-Cu(1) 120.9(2)

C(4)-O(5)-Cu(1)#1 124.47(19)

O(1)-C(1)-O(2) 125.1(3)

O(1)-C(1)-C(2) 117.3(3)

O(2)-C(1)-C(2) 117.7(3)

2, Henle reaction application

the preparation of 2-Nitro-1-phenylethanol

the preparation of 2-nitro-1 phenylethyl alcohol

Get 0.15mmol title complex (catalytic amount is 15%) in the little flask of 25mL, add the methanol solution of 2 milliliters, then, in above-mentioned solution, add the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL, stirring at normal temperature, reacts 72 hours, with sherwood oil/eluent methylene chloride, carry out column chromatography, transformation efficiency 80% ¹h NMR (300MHz, CDCl ₃) 7.28～7.32 (m, 5H, Ar-H), 5.32～5.35 (d, J=9.18Hz, 1H ,-CH), 4.38～4.56 (m, 2H ,-CH ₂), 3.89 (br, 1H ,-OH).

Claims

1. one kind by the copper complex shown in following chemical formula:

The synthetic method of this title complex, comprise and synthesize and separate, it is characterized in that: the described synthetic 1.9120g of measuring (0.01mol) N-(2-hydroxyethyl) phthalimide is put into 100ml round-bottomed flask, add 50ml anhydrous methanol, stirring is dissolved it, by 0.994g (0.005mol) Cu (OAc) ₂h ₂o adds above-mentioned solution, and after reflux 48h, heat filtering reaction soln, leaves standstill nature volatilization, separates out blue colored crystal.

2. the purposes of methanol acetic acid copper a metal-organic complex, it is characterized in that as catalyzer 0.148mmol, under phenyl aldehyde 0.10 mL (0.986 mmol) and Nitromethane 99Min. (0.50 mL, 9.255 mmol) room temperature, stir transformation efficiency 55.2 % in the Henle reaction of 72 h.