CN103641787A - Chiral oxazolinyl cobalt complex and synthesis method thereof - Google Patents

Chiral oxazolinyl cobalt complex and synthesis method thereof Download PDF

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CN103641787A
CN103641787A CN201310716820.6A CN201310716820A CN103641787A CN 103641787 A CN103641787 A CN 103641787A CN 201310716820 A CN201310716820 A CN 201310716820A CN 103641787 A CN103641787 A CN 103641787A
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complex
cobalt
oxazolinyl
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chlorobenzene
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罗梅
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract

The invention discloses a chiral oxazolinyl cobalt complex and synthesis method thereof. The chemical formula is shown in the specification. The synthesis method comprises the following steps: in the presence of 50.0mol% cobalt chloride hexahydrate serving as a catalyst and 50mL of chlorobenzene as a solvent, performing a reflux reaction on 20.0mmol of hydroxybenzonitrile and 4.4391g of D-phenylglycinol for 72 hours, purifying, removing chlorobenzene at then end of the reaction, dissolving with water, leaching by using chloroform, purifying by using column chromatography after a leaching phase is subjected to desolvation; preparing a saturated liquid by using trichloromethane/ethanol, and naturally volatilizing to obtain a chiral oxazolinyl cobalt complex monocrystal. The complex shows a certain catalyzing performance in Henry reactions of benzene and methanal and the yields respectively reach 88.4 percent.

Description

A kind of chiral oxazoline cobalt complex and synthetic method thereof
one, technical field
The present invention relates to a kind of organometallic complex (title complex) and preparation method thereof, particularly nitrogenous oxazoline a metal-organic complex and preparation method thereof, is exactly a kind of cobalt complex and synthetic method thereof of chirality phosphine acyl Shuan An oxazoline.
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, is 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.Shou bisoxazoline part one cobalt metal compounding synthetic has many bibliographical informations in recent years.
Reference:
1. NCN-Pincer Cobalt Complexes Containing Bis(oxazolinyl)phenyl Ligands,
Hosokawa, Satomi; Ito, Jun-ichi; Nishiyama, Hisao, Organometallics (2013), 32(14), 3980-3985;
2.Cyclopentadienyl 1,2- and 1,3-Disubstituted Cobalt Sandwich Compounds {η5-[MeOC(O)]2C5H3} Co(η4-C4Ph4): Precursors for Sterically Hindered Bidentate Chiral and Achiral Ligands, Singh, Nem; Elias, Anil J. , Organometallics (2012), 31(5), 2059-2065;
3. (Py)2Co(CH2SiMe3)2 As an easily accessible source of "CoR2" Zhu, Di; Janssen, Femke F. B. J.; Budzelaar, Peter H. M. , Organometallics (2010), 29(8), 1897-1908。
three, summary of the invention
The present invention aims to provide a kind of Co-N a metal-organic complex to be applied to catalytic field, and technical problem to be solved is selected Lin Qiang oxazolin as the copper complex of part synthesis of chiral bisoxazoline.
The cobalt complex of the Shou bisoxazoline that the present invention is alleged is a kind of be by salicylonitrile, D-benzene glycinol and cobalt chloride hexahydrate, prepared by the title complex shown in following chemical formula:
Figure 2013107168206100002DEST_PATH_IMAGE001
（Ⅰ）。
Chemical name: six 2-[4(R) and-phenyl-4,5-dihydro]-2-oxazolinyl } phenol cobalt complex, is called for short title complex (I).
This compound has shown certain catalytic performance in the Henle reaction of phenyl aldehyde, and its transformation efficiency is respectively 88.4 %.
This synthetic method comprises synthetic with separated, described synthetic 50.0 mol% that use, cobalt chloride hexahydrate is made catalyzer, salicylonitrile 20.0 mmol, D-benzene glycinol 4.4391 g, with 50mL chlorobenzene, make solvent, back flow reaction 72 hours, purifying, i.e. reaction is sloughed chlorobenzene after finishing, after being dissolved in water, with chloroform extraction, after extraction phase precipitation, use column chromatography purification; With trichloromethane/ethanol preparation saturated solution, chiral oxazoline cobalt complex monocrystal naturally volatilizees to obtain.
Building-up reactions is as follows:
Figure 182873DEST_PATH_IMAGE002
This synthetic method one step obtains target product, and technique is simple, easy to operate.
Four, accompanying drawing explanation
Fig. 1 tri-2-[4(R) and-phenyl-4,5-dihydro]-2-oxazolinyl } the X-diffraction analysis figure of phenol cobalt complex.
Five, embodiment
In 100mL two-mouth bottle, add cobalt chloride hexahydrate 2.3812g (10.0 mmol), 50mL chlorobenzene, salicylonitrile 2.3757g (20.0mmol), D-benzene glycinol 3.6798 g, by the mixture 72h that at high temperature refluxes, stopped reaction, by sherwood oil and eluent methylene chloride, column chromatography for separation, by the last component point nature complex monocrystal that volatilizees to obtain, productive rate 850 %, m.p.:176-178 ° of C, ultimate analysis: test value: C:67.23 %, H:4.70%, N:4.90 %; Calculated value: 67.30%, 4.48%, N, 5.23%; IR (KBr): 3061,3030,2965,1613,1550,1478,1441,1397,1339,1232,1157,1073,1057,999,952,939,856,749,698,581;
Match crystal volume data is as follows:
Empirical formula C90H72 N3O12 Co3
Molecular weight 1606.33
Temperature 140 (2) K
Wavelength 0.71073 A
Crystallographic system, spacer R3
Unit cell parameters a=19.092 (3) A alpha=90 deg.
b = 19.092(3) A beta = 90 deg.
c = 18.575(5) A gamma = 120 deg.
Volume 5864(2) A^3
Electric density 3,1.365 Mg/m^3
Absorption correction parameter 0.697 mm^-1
Number of electrons 2493 in unit cell
Crystallographic dimension 0.09 x 0.08x 0.06 mm
Scope 1.65 to 25.99 at Theta angle
Index capture range-23<=h<=23 of HKL ,-20<k<23-22<l<=22
Collection/independent diffraction data 14088/ 5154 [R (int)=0.1286]
Data integrity degree 100.0 % of theta=30.5
The method Multi Slice Mode of absorption correction
Transmitance 0.9594 and 0.9399 of minimax
The Matrix least square method of the method F^2 that refine is used
Number/the number of parameters 5154/4/334 of data number/use restriction
The method 0.883 that refine is used
The consistence factor R 1=0.0646 of point diffraction, wR2=0.1175
The identical factor R 1=0.1299 of observable diffraction, wR2=0.1368
Absolute configuration parameter 0.003(3)
Maximum summit on difference Fourier figure and peak valley 0.632 and-0.306e.A^-3
the typical bond distance's data of crystal:
Co(1)-O(2)#1 2.059(5)
Co(1)-O(2)#2 2.059(5)
Co(1)-O(2) 2.059(5)
Co(1)-O(1) 2.112(5)
Co(1)-O(1)#2 2.112(5)
Co(1)-O(1)#1 2.112(5)
Co(1)-Co(2) 2.823(3)
Co(1)-Co(3) 2.832(3)
Co(2)-O(1)#2 1.912(5)
Co(2)-O(1)#1 1.912(5)
Co(2)-O(1) 1.913(5)
Co(2)-N(1)#2 1.923(5)
Co(2)-N(1) 1.923(5)
Co(2)-N(1)#1 1.923(5)
Co(3)-O(2)#1 2.085(5)
Co(3)-O(2)#2 2.085(5)
Co(3)-O(2) 2.085(5)
Co(3)-N(2) 2.098(6)
Co(3)-N(2)#2 2.098(6)
Co(3)-N(2)#1 2.098(6)
the typical bond angle data of crystal:
O(2)#1-Co(1)-O(2)#2 79.0(2)
O(2)#1-Co(1)-O(2) 79.0(2)
O(2)#2-Co(1)-O(2) 79.0(2)
O(2)#1-Co(1)-O(1) 109.67(17)
O(2)#2-Co(1)-O(1) 99.95(16)
O(2)-Co(1)-O(1) 170.99(19)
O(2)#1-Co(1)-O(1)#2 99.95(16)
O(2)#2-Co(1)-O(1)#2 170.99(19)
O(2)-Co(1)-O(1)#2 109.67(17)
O(1)-Co(1)-O(1)#2 71.8(2)
O(2)#1-Co(1)-O(1)#1 170.99(19)
O(2)#2-Co(1)-O(1)#1 109.67(17)
O(2)-Co(1)-O(1)#1 99.95(16)
O(1)-Co(1)-O(1)#1 71.8(2)
O(1)#2-Co(1)-O(1)#1 71.8(2)
O(2)#1-Co(1)-Co(2) 132.72(14)
O(2)#2-Co(1)-Co(2) 132.71(14)
O(2)-Co(1)-Co(2) 132.71(14)
O(1)-Co(1)-Co(2) 42.64(13)
O(1)#2-Co(1)-Co(2) 42.64(13)
O(1)#1-Co(1)-Co(2) 42.64(13)
O(2)#1-Co(1)-Co(3) 47.28(14)
O(2)#2-Co(1)-Co(3) 47.29(14)
O(2)-Co(1)-Co(3) 47.29(14)
O(1)-Co(1)-Co(3) 137.36(13)
O(1)#2-Co(1)-Co(3) 137.36(13)
O(1)#1-Co(1)-Co(3) 137.36(13)
Co(2)-Co(1)-Co(3) 180.0
O(1)#2-Co(2)-O(1)#1 80.8(2)
O(1)#2-Co(2)-O(1) 80.8(2)
O(1)#1-Co(2)-O(1) 80.8(2)
O(1)#2-Co(2)-N(1)#2 93.5(2)
O(1)#1-Co(2)-N(1)#2 93.1(2)
O(1)-Co(2)-N(1)#2 172.2(2)
O(1)#2-Co(2)-N(1) 93.1(2)
O(1)#1-Co(2)-N(1) 172.2(2)
O(1)-Co(2)-N(1) 93.5(2)
N(1)#2-Co(2)-N(1) 92.1(2)
O(1)#2-Co(2)-N(1)#1 172.2(2)
O(1)#1-Co(2)-N(1)#1 93.5(2)
O(1)-Co(2)-N(1)#1 93.1(2)
N(1)#2-Co(2)-N(1)#1 92.1(2)
N(1)-Co(2)-N(1)#1 92.1(2)
O(1)#2-Co(2)-Co(1) 48.43(14)
O(1)#1-Co(2)-Co(1) 48.43(14)
O(1)-Co(2)-Co(1) 48.43(14)
N(1)#2-Co(2)-Co(1) 123.75(17)
N(1)-Co(2)-Co(1) 123.75(17)
N(1)#1-Co(2)-Co(1) 123.75(17)
O(2)#1-Co(3)-O(2)#2 77.9(2)
O(2)#1-Co(3)-O(2) 77.9(2)
O(2)#2-Co(3)-O(2) 77.9(2)
O(2)#1-Co(3)-N(2) 98.5(2)
O(2)#2-Co(3)-N(2) 163.3(2)
O(2)-Co(3)-N(2) 85.4(2)
O(2)#1-Co(3)-N(2)#2 163.3(2)
O(2)#2-Co(3)-N(2)#2 85.4(2)
O(2)-Co(3)-N(2)#2 98.5(2)
N(2)-Co(3)-N(2)#2 97.4(2)
O(2)#1-Co(3)-N(2)#1 85.4(2)
O(2)#2-Co(3)-N(2)#1 98.5(2)
O(2)-Co(3)-N(2)#1 163.3(2)
N(2)-Co(3)-N(2)#1 97.4(2)
N(2)#2-Co(3)-N(2)#1 97.5(2)
O(2)#1-Co(3)-Co(1) 46.52(14)
O(2)#2-Co(3)-Co(1) 46.52(14)
O(2)-Co(3)-Co(1) 46.52(14)
N(2)-Co(3)-Co(1) 119.80(17)
N(2)#2-Co(3)-Co(1) 119.80(17)
N(2)#1-Co(3)-Co(1) 119.80(17)
Henle reaction application
2-nitro-1-phenylethyl alcohol
Figure 2013107168206100002DEST_PATH_IMAGE003
Catalyst I (0.148mmol), phenyl aldehyde 0.10 mL (0.986 mmol) and Nitromethane 99Min. (0.50 mL, 9.255 mmol) at room temperature stir 3 days, with nuclear-magnetism monitoring, transformation efficiency: 88.4 %, 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 (3)

1. one kind six 2-[4(R)-phenyl-4,5-dihydro]-2-oxazolinyl phenol cobalt complex, it is characterized in that: by salicylonitrile, D-benzene glycinol and cobalt chloride hexahydrate, prepared, by the title complex shown in following chemical formula:
Figure 2013107168206100001DEST_PATH_IMAGE002
（Ⅰ）。
2. title complex claimed in claim 1 (I), at 140(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) 2 (1) 2 (1), unit cell parameters: a=19.092 (3) A, alpha=90 deg; B=19.092 (3), beta=90 deg.; C=18.575 (5), gamma=90 deg.
3. the synthetic method of title complex claimed in claim 1 (I), comprise synthetic with separated, described synthetic use 50.0 mol% cobalt chloride hexahydrates are made catalyzer, salicylonitrile 20.0 mmol, D-benzene glycinol 4.4391 g, with 50mL chlorobenzene, make solvent, back flow reaction 72 hours, purifying, i.e. reaction is sloughed chlorobenzene after finishing, after being dissolved in water, with chloroform extraction, after extraction phase precipitation, use column chromatography purification; With trichloromethane/ethanol preparation saturated solution, chiral oxazoline cobalt complex monocrystal naturally volatilizees to obtain.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105001268A (en) * 2015-08-13 2015-10-28 合肥祥晨化工有限公司 Chiral oxazoline platinum complex crystal and synthetic method thereof
CN105237413A (en) * 2015-10-30 2016-01-13 合肥祥晨化工有限公司 Chiral crystal-water-containing phenylglycinol cobalt complex
CN107337652A (en) * 2017-07-05 2017-11-10 合肥祥晨化工有限公司 A kind of Chiral oxazoline cobalt complex and purposes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999038857A2 (en) * 1998-01-30 1999-08-05 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Method for producing 5-alkoxy (or 5-aroxy)-2,3-dihydrofuran-2-ones
CN102267954A (en) * 2011-06-13 2011-12-07 罗梅 Chiral oxazoline and synthetic method thereof
CN102311405A (en) * 2010-07-07 2012-01-11 三星移动显示器株式会社 Organic materials and the organic light-emitting device that comprises this organic materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999038857A2 (en) * 1998-01-30 1999-08-05 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Method for producing 5-alkoxy (or 5-aroxy)-2,3-dihydrofuran-2-ones
CN102311405A (en) * 2010-07-07 2012-01-11 三星移动显示器株式会社 Organic materials and the organic light-emitting device that comprises this organic materials
CN102267954A (en) * 2011-06-13 2011-12-07 罗梅 Chiral oxazoline and synthetic method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105001268A (en) * 2015-08-13 2015-10-28 合肥祥晨化工有限公司 Chiral oxazoline platinum complex crystal and synthetic method thereof
CN105237413A (en) * 2015-10-30 2016-01-13 合肥祥晨化工有限公司 Chiral crystal-water-containing phenylglycinol cobalt complex
CN107337652A (en) * 2017-07-05 2017-11-10 合肥祥晨化工有限公司 A kind of Chiral oxazoline cobalt complex and purposes

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