CN109180709A - (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex and preparation method - Google Patents
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex and preparation method Download PDFInfo
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- CN109180709A CN109180709A CN201811183587.9A CN201811183587A CN109180709A CN 109180709 A CN109180709 A CN 109180709A CN 201811183587 A CN201811183587 A CN 201811183587A CN 109180709 A CN109180709 A CN 109180709A
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- pyridine
- firpene
- pyridyl group
- hexafluoroacetylacetone
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 66
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000013110 organic ligand Substances 0.000 claims abstract description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 10
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- KMRMUZKLFIEVAO-IUCAKERBSA-N (1s,5r)-6,6-dimethylbicyclo[3.1.1]hept-3-ene-4-carbaldehyde Chemical compound C1[C@@H]2C(C)(C)[C@H]1CC=C2C=O KMRMUZKLFIEVAO-IUCAKERBSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 claims description 5
- 240000005125 Myrtus communis Species 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- JTABHYSLUVGCPP-UHFFFAOYSA-N CC(=O)C.C(C)(=O)F Chemical compound CC(=O)C.C(C)(=O)F JTABHYSLUVGCPP-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 150000001879 copper Chemical class 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 150000004699 copper complex Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 230000005294 ferromagnetic effect Effects 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 2,4-pentanedione copper complex Chemical class 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 210000003739 neck Anatomy 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000002983 circular dichroism Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- 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
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses one kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex and preparation method, the molecular formula of complex is Cu3(hfac)6(L)2, the present invention is by the nitrogenous chirality organic ligand L:[(- of monodentate) -2- (4 '-pyridyl group) -4,5- firpene-pyridine] with Cu (hfac)2·2H2O reaction, obtained (-) -2- (4 '-pyridyl group) -4, the preparation method of chiral three core copper complexes of 5- firpene-pyridine hexafluoroacetylacetone, simple process, avoid prepare complex pass through frequently with high temperature and pressure the issuable security risk of solvent thermal process, and easy post-processing, yield are high.The complex synthesis condition is mild, yield is high, it is easy to isolate and purify, chiral asymmetry catalysis, chiral enantiomer separation and chiral induction and it is magnetic-light in terms of have broad application prospects.
Description
Technical field
The invention belongs to molecule base chirality function material and its preparation and application technical fields, in particular to a kind of to have
Chiral optical activity has ferromagnetic three core copper complex and preparation method thereof again.
Background technique
Since chiral coordination compound is in chiral asymmetric catalysis, the separation of chipal compounds, chiral probe and chirality
Induction etc. have a wide range of applications, therefore chiral coordination compound design and prepare always Coordinative Chemistry and material science neck
The research topic of domain hot topic.Chirality is introduced especially in the molecular structure of magnetic partner, exists simultaneously chiral and magnetism
In the same molecule, both different properties interact in the molecule, can generate interesting magnetic chirality color to effect.From
And assign this kind of functional complexes has tempting application prospect in terms of magnetic-light spin electric device, causes to synthesize chemist
With the great research interest of material scholars.Since the synthesis difficulty of chiral ligand is big, yield is not high, therefore chiral coordination compound
Quantity is relatively fewer, and has chiral and Ferromagnetic coupling complex more rare simultaneously.Currently, having chiral optical activity
Three core copper complexes of ferromagnetic property are shown simultaneously there is not yet document report, more without relevant license.
Summary of the invention
The object of the present invention is to provide one kind to have ferromagnetic (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoro
Acetylacetone,2,4-pentanedione copper complex and preparation method thereof, the complex are that molecule base chirality function material is (-) -2- (4 '-pyridyl group) -
Chiral three core copper complexes of 4,5- firpenes-pyridine hexafluoroacetylacetone, preparation method simple process, easy post-processing and yield
It is high.
To achieve the above object, the invention adopts the following technical scheme:
One kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex, (-) -2-
(4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex molecular formula is Cu3(hfac)6(L)2, wherein hfac
For hexafluoroacetylacetone, molecular formula CF3COCH2COCF3；L is [(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine], structure
Formula is
The preparation of chiral three core copper complexes of one kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone
Method, steps are as follows:
(1) as the intermediate Cu (hfac) of reaction raw materials2·2H2The preparation of O: hexafluoroacetylacetone is soluble in water, room
Temperature lower stirring 5~10 minutes, the aqueous solution of hexafluoroacetylacetone is obtained, lower addition ammonium hydroxide is then slowly stirred, then Cu is added dropwise
(CH3COO)2·H2The aqueous solution of O, have precipitating generate, after filtering will precipitating washing, be dried in vacuo green product is Cu
(hfac)2·2H2O；
(2) chiral three core copper complexes of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone
Cu3(hfac)6(L)2Preparation: will be dissolved with Cu (hfac)2·2H2The normal octane of O and chiral monodentate containing n-donor ligand L are molten
Liquid is added in 100mL round-bottomed flask, is heated to flow back 3 hours at 130 DEG C, then cooled to room temperature, filtering, and gained is clear
Clear solution stands volatilization, obtains blue-green diamond shaped transparent crystal within about 2~3 days.Filtering, vacuum drying obtain (-) -2- (4 '-pyrroles
Piperidinyl) chiral three core copper complexes of -4,5- firpene-pyridine hexafluoroacetylacetone.
Cu (CH in the step (1)3COO)2·H2Cu (CH in the aqueous solution of O3COO)2·H2The concentration of O be 1~
1.5mol/L。
The concentration of hexafluoroacetylacetone is 1.5~2mol/L in the aqueous solution of hexafluoroacetylacetone in the step (1).
Hexafluoroacetylacetone and Cu (CH used in the step (1)3COO)2·H2The ratio between amount of substance of O is 2:1,
On the basis of 1mmol hexafluoroacetylacetone, needing concentration is the ammonium hydroxide 1mL of 1mol/L.
Cu (hfac) in the step (2)2·2H2In the normal octane solution of O, Cu (hfac)2·2H2The concentration of O is
0.003~0.005mol/L.
In the step (2) in the dichloromethane solution of chirality organic ligand containing N L, the concentration of the chiral L of organic ligand containing N
For 0.003~0.005mol/L.
Cu (hfac) in the step (2)2·2H2The ratio between the amount of substance of O and the chiral L of organic ligand containing N are 1:1.
The nitrogenous organic ligand L:(- of monodentate chiral in the step (2)) -2- (4 '-pyridyl group) -4,5- firpene-pyridine
The preparation method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.5 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
With 20~25mL pyridinium dissolution round-bottomed flask will be added dissolved with 18~20mL pyridine solution of 15~18 grams of iodine in acetylpyridine
In, mixture is heated to 100~110 DEG C, reacts 4~4.5 hours, then cools to room temperature and filter, and is rushed with a small amount of pyridine
Wash secondary, intermediate needed for gray solid is obtained after vacuum drying as；
B. the nitrogenous organic ligand L:(- of monodentate chiral) synthesis of -2- (4 '-pyridyl group) -4,5- firpene-pyridine: weigh step
3.8 grams of 4- (pyridine acetyl group) the pyridinium iodide intermediate and 2.0~2.8 grams of ammonium acetate (NH that rapid a is prepared4Ac it) is placed in
In three-neck flask, the formamide (CH of 40~48mL is added3CONH2).It is stirred continuously the lower myrte for being added 2.5 grams
(-)-myrtenal (production of Alfa company).It is heated to 75-85 DEG C, is reacted 12-12.5 hours under nitrogen.Above-mentioned product is filtered
Off-white solid is obtained, and is rinsed with water, it is then that solid is dry with ethyl alcohol recrystallization.
Beneficial effects of the present invention: (1) of the invention by a kind of nitrogenous chirality organic ligand L:[(- of monodentate) -2- (4 '-pyridines
Base) -4,5- firpene-pyridine] and Cu (hfac)2·2H2O reaction, obtained (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine
Hexafluoroacetylacetone chirality three core copper complexes preparation method, simple process, avoid prepare complex pass through frequently with height
The issuable security risk of the solvent thermal process of warm high pressure, and easy post-processing, yield are high.(2) performance test shows: this hair
Chiral three core copper complexes of (-) -2- (4 '-pyridyl group) -4,5- firpene of bright preparation-pyridine hexafluoroacetylacetone have hand simultaneously
Property optical activity and ferromagnetic coupling performance.(3) the chirality trinuclear complex have synthesis condition is mild, yield is high, stability is strong,
Reproducibility is good, it is easy to isolate and purify, chiral asymmetry catalysis, chiral enantiomer separation and chiral induction and it is magnetic-light from
Rotation electronic device etc. has broad application prospects.
Detailed description of the invention
Fig. 1 is the chiral three core copper cooperation of embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone
Object Cu3(hfac)6(L)2Molecular structure；
Fig. 2 is the chiral three core copper cooperation of embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone
Object Cu3(hfac)6(L)2Circular dichroism figure；
Fig. 3 is the chiral three core copper cooperation of embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone
Object Cu3(hfac)6(L)2DC magnetic susceptibility and temperature product variation with temperature relational graph.
Specific embodiment
Embodiment 1
(-) -2- (4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3(hfac)6
(L)2Preparation method, steps are as follows:
(1) as the intermediate Cu (hfac) of reaction raw materials2·2H2The preparation of O: by 6.25 grams of hexafluoroacetylacetones
(hfac, 0.03mol, the production of lark prestige Reagent Company) is dissolved in 15mL water and stirs 5 minutes, forms clear solution.Then add
The ammonium hydroxide for entering 30mL 1M, is slowly stirred down, and 10mL is added dropwise dissolved with 3.0 grams of Cu (CH3COO)2·H2O's (0.015mol) is water-soluble
Liquid has green precipitate generation, washes precipitating after filtering, is dried in vacuo to obtain product Cu (hfac)2·2H2O, yield are about 92%
(being calculated by Cu).Elemental analysis: molecular formula C is pressed10H6O6F12Cu (molecular weight 513.68): calculated value (%) C, 23.38；H,
1.18.Measured value (%) C, 23.45；H,1.13.
(2) (-) -2- (4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3
(hfac)6(L)2Preparation: Cu (hfac) is sequentially added in 100mL round-bottomed flask2·2H2O (25.7mg, 0.05mmol) and
The nitrogenous organic ligand L:(- of monodentate chiral) -2- (4 '-pyridyl group) -4,5- firpene-pyridine (12.5mg, 0.05mmol), then will
The normal octane of 10mL is added thereto the solvent as reactant.It persistently stirs lower 130 DEG C to flow back 3 hours, then naturally cool to
Room temperature, filtering, gained clear solution stand volatilization, and blue-green diamond shaped transparent crystal is obtained after 3 days.Filtering, is dried in vacuo to obtain the final product
To chiral three core copper complexes of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone.Calculating yield is 89%
(being calculated by Cu).
Using 2400 elemental analyser of Perkin-Elmer to (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoro
Three core copper complex Cu of acetylacetone,2,4-pentanedione chirality3(hfac)6(L)2The content analysis of C, H and N are carried out, by molecular formula
C64H42N4O12F36Cu3(molecular weight 1933.63) calculated value (%): C, 39.75；H,2.19；N,2.90.Measured value (%): C,
39.82；H,2.13；N 2.81.Using Bruker SMART APEX CCD diffractometer single crystal diffractometer in room temperature
Under determine (-) -2- (4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3(hfac)6
(L)2Molecular structure (see Fig. 1).In three core copper complex of chirality, two Cu (II) ion having the same 5 therein
It is coordinated CuNO4Trigonal biyramid geometric configuration.Two hfac ligands respectively provide two O atoms and each Cu (II) ion chelating, match
Position N atom is provided by the nitrogenous chirality organic ligand L of monodentate.In addition 4 coordination CuO are presented in Cu (II) ion4Plane four
Side shape, 4 O atoms are provided by two hfac ligands respectively.Therefore, three Cu (II) ions in the three core steel structure of chirality are aobvious
Two different coordination geometric configurations are shown.(-) -2- has been measured using Biologic MS-500spectropolarimeter
(4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3(hfac)6(L)2Circular dichroism light
Spectrum, as shown in Fig. 2, very strong exciton coupled signal is presented in the complex at λ=310 and 330nm, respectively corresponds negative, positive
Cotton effect, it was demonstrated that three core copper complexes have very strong chiral optical activity.
(-) -2- (4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3(hfac)6
(L)2Magnetism testing:
(-) -2- is tested using Quantum Design MPMS-XL5SQUID Magnetometer magnetic measurement instrument
(4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3(hfac)6(L)2Dc magnetization
Rate.Test result shows: the chiral binuclear copper complex Cu of acetate bridging2(CH3COO)4(L)2Temperature 300-2.0K it
Between, the product of molar susceptibility and temperature slowly increases (shown in Fig. 3) with the reduction of temperature, absolutely proves the center Cu (II)
There are apparent Ferromagnetic couplings.
The present embodiment chiral monodentate organic ligand L:(- containing N) -2- (4 '-pyridyl group) -4,5- firpene-pyridine preparation side
Method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.5 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine is dissolved with 22mL pyridine solution, will be added in round-bottomed flask dissolved with the 19mL pyridine solution of 16 grams of iodine, mixture adds
Heat reacts 4 hours to 105 DEG C, then cools to room temperature and filter, secondary with a small amount of pyridine flushing, obtains after vacuum drying grey
Color solid is required intermediate；
B. chiral monodentate organic ligand L:(- containing N) synthesis of -2- (4 '-pyridyl group) -4,5- firpene-pyridine: weigh step
3.8 grams of 4- (pyridine acetyl group) the pyridinium iodide intermediate and 2.5 grams of ammonium acetate (NH that a is prepared4Ac) it is placed in three necks burning
In bottle, the formamide (CH of 45mL is added3CONH2), it is stirred continuously lower myrte (-)-myrtenal for being added 2.5 grams,
80 DEG C are heated to, is reacted 12 hours under nitrogen, Off-white solid is obtained by filtration in above-mentioned product, and be rinsed with water, with ethyl alcohol weight
Crystallization, it is then that solid is dry.Yield is 85% (calculating by intermediate).Elemental analysis: molecular formula C is pressed17H18N2: calculated value
(%): C, 81.56；H,7.25；N,11.19；Measured value (%): C, 81.61；H,7.32；N,11.27.Infrared spectroscopy IR
(KBr):2948(s),2993(m),2866(v),1582(m),1459(s),1385(m),780(m),757(s)。
Embodiment 2
Chiral three core copper complexes of the present embodiment (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone
Cu3(hfac)6(L)2Preparation method, steps are as follows:
(1) as the intermediate Cu (hfac) of reaction raw materials2·2H2The preparation of O: by 6.25 grams of hexafluoroacetylacetones
(hfac, 0.03mol, the production of lark prestige Reagent Company) is dissolved in 20mL water and stirs 10 minutes, forms clear solution.Then add
The ammonium hydroxide for entering 30mL 1M, is slowly stirred down, and 15mL is added dropwise dissolved with 3.0 grams of Cu (CH3COO)2·H2O's (0.015mol) is water-soluble
Liquid has green precipitate generation, washes precipitating after filtering, is dried in vacuo to obtain product Cu (hfac)2·2H2O；
(2) (-) -2- (4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3
(hfac)6(L)2Preparation: Cu (hfac) is sequentially added in 100mL round-bottomed flask2·2H2O (25.7mg, 0.05mmol) and
The nitrogenous organic ligand L:(- of monodentate chiral) -2- (4 '-pyridyl group) -4,5- firpene-pyridine (12.5mg, 0.05mmol), then will
The normal octane of 15mL is added thereto the solvent as reactant.It persistently stirs lower 130 DEG C to flow back 3 hours, then naturally cool to
Room temperature, filtering, gained clear solution stand volatilization, obtain blue-green diamond shaped transparent crystal within about 2 days.Filtering, is dried in vacuo to obtain the final product
To chiral three core copper complexes of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone.
The present embodiment chirality organic ligand L:(- containing N) -2- (4 '-pyridyl group) -4,5- firpene-pyridine preparation method is such as
Under:
A.4- in the round-bottomed flask of 250mL, 4.5 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine is dissolved with 20mL pyridine solution, will be added in round-bottomed flask dissolved with the 18mL pyridine solution of 15 grams of iodine, mixture adds
Heat reacts 4.5 hours to 100 DEG C, then cools to room temperature and filter, secondary with a small amount of pyridine flushing, after vacuum drying
Gray solid is required intermediate；
B. chirality organic ligand L:(- containing N) synthesis of -2- (4 '-pyridyl group) -4,5- firpene-pyridine: weigh step a system
Standby obtained 3.8 grams of 4- (pyridine acetyl group) pyridinium iodide intermediate and 2.0 grams of ammonium acetate (NH4Ac) it is placed in three-neck flask
In, add the formamide (CH of 40mL3CONH2), it is stirred continuously lower myrte (-)-myrtenal (hundred for being added 2.5 grams
The production of Ling Wei company), 75 DEG C are heated to, is reacted 12.5 hours under nitrogen, Off-white solid is obtained by filtration in above-mentioned product, is used in combination
Water rinses, then that solid is dry with ethyl alcohol recrystallization, obtains the chiral L of organic ligand containing N.
Embodiment 3
Chiral three core copper complexes of the present embodiment (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone
Cu3(hfac)6(L)2Preparation method, steps are as follows:
(1) as the intermediate Cu (hfac) of reaction raw materials2·2H2The preparation of O: by 6.25 grams of hexafluoroacetylacetones
(hfac, 0.03mol, the production of lark prestige Reagent Company) is dissolved in 18mL water and stirs 8 minutes, forms clear solution.Then add
The ammonium hydroxide for entering 30mL 1M, is slowly stirred down, and 12mL is added dropwise dissolved with 3.0 grams of Cu (CH3COO)2·H2O's (0.015mol) is water-soluble
Liquid has green precipitate generation, washes precipitating after filtering, is dried in vacuo to obtain product Cu (hfac)2·2H2O；
(2) (-) -2- (4 '-pyridyl group) -4,5- firpene-three core copper complex Cu of pyridine hexafluoroacetylacetone chirality3
(hfac)6(L)2Preparation: Cu (hfac) is sequentially added in 100mL round-bottomed flask2·2H2O (25.7mg, 0.05mmol) and
The nitrogenous organic ligand L:(- of monodentate chiral) -2- (4 '-pyridyl group) -4,5- firpene-pyridine (12.5mg, 0.05mmol), then will
The normal octane of 12mL is added thereto the solvent as reactant.It persistently stirs lower 130 DEG C to flow back 3 hours, then naturally cool to
Room temperature, filtering, gained clear solution stand volatilization, obtain blue-green diamond shaped transparent crystal within about 3 days.Filtering, is dried in vacuo to obtain the final product
To chiral three core copper complexes of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone.
The present embodiment chiral monodentate organic ligand L:(- containing N) -2- (4 '-pyridyl group) -4,5- firpene-pyridine preparation side
Method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.5 grams of 4- the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine is dissolved with 25mL pyridine solution, will be added in round-bottomed flask dissolved with the 20mL pyridine solution of 18 grams of iodine, mixture adds
Heat reacts 4 hours to 110 DEG C, then cools to room temperature and filter, secondary with a small amount of pyridine flushing, obtains after vacuum drying grey
Color solid is required intermediate；
B. chiral monodentate organic ligand L:(- containing N) synthesis of -2- (4 '-pyridyl group) -4,5- firpene-pyridine: weigh step
3.8 grams of 4- (pyridine acetyl group) the pyridinium iodide intermediate and 2.8 grams of ammonium acetate (NH that a is prepared4Ac) it is placed in three necks burning
In bottle, the formamide (CH of 48mL is added3CONH2), it is stirred continuously lower myrte (-)-myrtenal for being added 2.5 grams,
85 DEG C are heated to, is reacted 12 hours under nitrogen, Off-white solid is obtained by filtration in above-mentioned product, and be rinsed with water, with ethyl alcohol weight
Crystallization, it is then that solid is dry, obtain chiral monodentate organic ligand containing N L.
Claims (8)
1. one kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex, (-) -2- (4 ' -
Pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex molecular formula be Cu3(hfac)6(L)2, wherein hfac is six
Acetyl fluoride acetone, molecular formula CF3COCH2COCF3；L is [(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine], and structural formula is
2. (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex according to claim 1
Preparation method, it is characterised in that steps are as follows:
(1) intermediate Cu (hfac)2·2H2The preparation of O: hexafluoroacetylacetone is soluble in water, it stirs 5~10 minutes at room temperature,
The aqueous solution of hexafluoroacetylacetone is obtained, is then slowly stirred lower addition ammonium hydroxide, then Cu (CH is added dropwise3COO)2·H2O's is water-soluble
Liquid, have precipitating generate, after filtering will precipitating washing, be dried in vacuo green product is Cu (hfac)2·2H2O；
(2) (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex Cu3(hfac)6(L)2System
It is standby: will be dissolved with Cu (hfac)2·2H2The normal octane solution of O and chiral monodentate containing n-donor ligand L are added in 100mL round-bottomed flask,
It is heated to flow back 3 hours at 130 DEG C, then cooled to room temperature, filter, gained clear solution stands volatilization, obtains within 2~3 days
Blue-green diamond shaped transparent crystal, filtering, vacuum drying obtain (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoro acetyl
Acetone copper complex.
3. (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex according to claim 2
Preparation method, it is characterised in that: Cu (CH in the step (1)3COO)2·H2Cu (CH in the aqueous solution of O3COO)2·H2O's
Concentration is 1~1.5mol/L, and the concentration of hexafluoroacetylacetone is 1.5~2mol/L, ammonia in the aqueous solution of hexafluoroacetylacetone
The concentration of water is 1mol/L.
4. (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex according to claim 2
Preparation method, it is characterised in that: hexafluoroacetylacetone and Cu (CH used in the step (1)3COO)2·H2The substance of O
The ratio between amount be 2:1, on the basis of 1mmol hexafluoroacetylacetone, needing concentration is the ammonium hydroxide 1mL of 1mol/L.
5. (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex according to claim 2
Preparation method, it is characterised in that: Cu (hfac) in the step (2)2·2H2In the normal octane solution of O, Cu (hfac)2·
2H2The concentration of O is 0.003~0.005mol/L.
6. (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex according to claim 2
Preparation method, it is characterised in that: in the step (2) in the normal octane solution of chirality organic ligand containing N L, chirality containing N it is organic
The concentration of ligand L is 0.003~0.005mol/L.
7. (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex according to claim 2
Preparation method, it is characterised in that: Cu (hfac) in the step (2)2·2H2The amount of the substance of O and the chiral L of organic ligand containing N
The ratio between be 1:1.
8. (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine hexafluoroacetylacetone copper complex according to claim 2
Preparation method, it is characterised in that: the nitrogenous organic ligand L:(- of monodentate chiral in the step (2)) -2- (4 '-pyridyl group) -4,
5- firpene-pyridine the preparation method is as follows:
A.4- in the round-bottomed flask of 250mL, 4.5 grams of 4- acetyl the preparation of (pyridine acetyl group) pyridinium iodide intermediate: are added
Yl pyridines will be added in round-bottomed flask dissolved with 18~20mL pyridine solution of 15~18 grams of iodine, be mixed with 20~25mL pyridinium dissolution
It closes object and is heated to 100~110 DEG C, react 4~4.5 hours, then cool to room temperature and filter, rinse secondary, vacuum with pyridine
Intermediate needed for gray solid is is obtained after drying；
B. the nitrogenous organic ligand L:(- of monodentate chiral) synthesis of -2- (4 '-pyridyl group) -4,5- firpene-pyridine: weigh step a system
Standby obtained 3.8 grams of 4- (pyridine acetyl group) pyridinium iodide intermediate and 2.0~2.8 grams of ammonium acetates are placed in three-neck flask,
Add the formamide (CH of 40~48mL3CONH2), it is stirred continuously lower myrte (-)-myrtenal for being added 2.5 grams,
It is heated to 75-85 DEG C, is reacted 12-12.5 hours under nitrogen, Off-white solid is obtained by filtration in above-mentioned product, and be rinsed with water,
It is then that solid is dry with ethyl alcohol recrystallization, obtain the nitrogenous organic ligand L of monodentate chiral.
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