CN109232616A - (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex and preparation method thereof - Google Patents
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex and preparation method thereof Download PDFInfo
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- pyridine
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 89
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 41
- 239000004332 silver Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000013110 organic ligand Substances 0.000 claims abstract description 27
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims abstract description 22
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 14
- 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
- 239000000243 solution Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 Acyl pyridine Chemical compound 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
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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 4
- 239000000126 substance Substances 0.000 claims description 4
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 230000003287 optical effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 239000005695 Ammonium acetate Substances 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002983 circular dichroism Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- KMRMUZKLFIEVAO-UHFFFAOYSA-N 7,7-dimethylbicyclo[3.1.1]hept-3-ene-4-carbaldehyde Chemical compound C1C2C(C)(C)C1CC=C2C=O KMRMUZKLFIEVAO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 125000001814 trioxo-lambda(7)-chloranyloxy group Chemical group *OCl(=O)(=O)=O 0.000 description 1
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- 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
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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Abstract
The invention discloses one kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex, the molecular formula of complex is [Ag (L) ClO4]∞, the present invention is by chiral monodentate organic ligand L:[(- containing N) -2- (4 '-pyridyl group) -4,5- firpene-pyridine] and AgClO4Reaction, obtained (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex preparation method, simple process, normal temperature and pressure reaction, safety is good and at low cost, easy post-processing and yield is up to 86%；The complex, which not only has chiral optical activity also, has absorption ultraviolet light, generate the ability of VISIBLE LIGHT EMISSION, it is the bifunctional material simultaneously with chiral optical activity and light transfer capability, is expected to have wide commercial applications prospect in terms of circular polarised luminescence, fluoroimmunoassay, nonlinear optical material and light shifting molecular as advanced luminescent material.
Description
Technical field
The invention belongs to inorganic-organic hybridization chirality function material and its preparation and application technical field, in particular to one
Kind has the chiral silver complex and preparation method thereof of visible light luminescent properties.
Background technique
Chirality is the essential attribute of substance, is played an important role in biology, pharmaceutical chemistry and material science.It is chiral
The design and synthesis of structure are always for a long time interesting project, have attracted the extensive pass of many research field researchers
Note, not just merely because they have important feature relevant to biology, as well as chiral material nonlinear optics,
It asymmetry catalysis, enantio-selectivity absorption and separates etc. with wide commercial applications prospect.
In transient metal complex, d10The silver complex of electron configuration has unique luminescent properties, is a kind of important
Molecule based luminescent material, become the research topic of Coordinative Chemistry and materials science field hot topic.Especially match in luminous silver
It closes and introduces chirality in object, it is also possible to assign some physical properties relevant and interesting to chirality of this kind of luminescent material such as: chiral
Circular polarised luminescence, chiral fluorescence probe, chiral induction etc., are potential multifunctional materials.This kind of material designs and prepares more
It is synthesis chemist and material supply section scholars are extremely interested and challenging research topic.
Summary of the invention
The object of the present invention is to provide one kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complexes to shine
Material and preparation method, the preparation method simple process, normal-temperature reaction, easy post-processing and yield are high.
To achieve the above object, the invention adopts the following technical scheme:
One kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex, (-) -2- (4 '-pyridyl group) -4,
5- firpene-pyridine chirality silver complex molecular formula is [Ag (L) ClO4] ∞, wherein L is chiral monodentate organic ligand containing N: (-)-
2- (4 '-pyridyl group) -4,5- firpene-pyridine, structural formula are。
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex preparation method, steps are as follows:
It (1) will be dissolved with silver perchlorate AgClO4Methanol solution be put into test tube as bottom, wherein the concentration of silver perchlorate is
0.01~0.02 mol/L；
(2) 6 ~ 8 mL of mixed solution of methanol and methylene chloride is added on bottom as intermediate buffer layer；
(3) will be dissolved with chiral monodentate organic ligand L:(- containing N) -2- (4 '-pyridyl group) -4,5- firpene-pyridine methylene chloride is molten
Liquid is slowly added in test tube as top layer, and wherein the concentration of chiral monodentate organic ligand containing N L is 0.01 ~ 0.02 mol/L；It should
There is blocky clear crystal in test tube after standing 4-5 days at room temperature, filtering, uses methanol and water washing respectively, and drying at room temperature is to get arriving
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4] ∞；
The bottom, intermediate buffer layer and the volume ratio of top layer are (4 ~ 7): (6 ~ 9): (4 ~ 7).
The volume ratio of methanol and methylene chloride is 1:2 in the mixed solution of methanol and methylene chloride in the step (2).
Described two reactant A gClO4It is 1:1 with the ratio between the amount of substance of chiral monodentate organic ligand containing N L.
Chiral monodentate organic ligand L:(- containing N in the step (3)) -2- (4 '-pyridyl group) -4,5- firpene-pyridine system
Preparation Method is as follows:
A. in the round-bottomed flask of 250 mL, 5.3 grams of 4- second the preparation of 4- (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine will be added in round-bottomed flask with 25 ~ 30 mL pyridinium dissolutions dissolved with 20 ~ 25 mL pyridine solutions of 18 ~ 21 grams of iodine,
Mixture is heated to 100 ~ 110 DEG C, reacts 4 ~ 4.5 hours, then cools to room temperature and filter, and rinses two with a small amount of pyridine
It is secondary, intermediate needed for gray solid is is obtained after vacuum drying；
B. chiral monodentate organic ligand L:(- containing N) synthesis of -2- (4 '-pyridyl group) -4,5- firpene-pyridine: weigh step a system
Standby obtained 4.2 grams of 4- (pyridine acetyl group) pyridinium iodide intermediate and 2.5 ~ 3.2 grams of ammonium acetate (NH4Ac three necks) are placed in
In flask, the formamide (CH of 45 ~ 50 mL is added3CONH2).It is stirred continuously the lower myrte (-)-for being added 2.8 grams
Myrtenal (Bellingwell company's production) is heated to 75-85 DEG C, reacts 12-12.5 hours under nitrogen, above-mentioned product is filtered
Obtain Off-white solid, and be rinsed with water, with ethyl alcohol recrystallization, then by solid be dried in vacuo chiral monodentate is matched containing N is organic
Body L.
Beneficial effects of the present invention: (1) of the invention by a kind of chiral monodentate organic ligand L:[(- containing N) -2- (4 '-pyridines
Base) -4,5- firpene-pyridine] and AgClO4Reaction, obtained (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver are matched
The preparation method of object is closed, simple process, normal temperature and pressure reaction, safety is good and at low cost, easy post-processing and yield is up to
86%；(2) (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex prepared by the present invention not only has chiral light
Learning activity also has absorption ultraviolet light, generates the ability of VISIBLE LIGHT EMISSION, has chiral optical activity while being extremely rare
With the bifunctional material of light transfer capability.(3) the chirality luminescent material is with synthesis condition is mild, yield is high, stability is strong, can
Favorable reproducibility isolates and purifies easy, is expected to as advanced luminescent material in circular polarised luminescence, fluoroimmunoassay, nonlinear optical
Learning material and light shifting molecular device etc. has wide commercial applications prospect.
Detailed description of the invention
Fig. 1 is embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]n's
Ag (I) ion coordination environment map, for clarity, H atom has been omitted from.
Fig. 2 is embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]n's
Two dimensional layer molecule structure chart, for clarity, H atom has been omitted from.
Fig. 3 is embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nHair
The launching light spectrogram of luminescent material.
Fig. 4 is embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nHair
The exciting light spectrogram of luminescent material.
Fig. 5 is embodiment 1 (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nHair
The chiral circular dichroism figure of luminescent material.
Specific embodiment
Embodiment 1
The present embodiment (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nPreparation side
Method, steps are as follows:
It (1) will be dissolved with AgClO4The methanol solution (4 mL) of (0.08 mmol, 16.6 mg) is seated in the bottom of test tube；
(2) mixed solution (the volume ratio CH of 6 mL methanol and methylene chloride is then added3OH : CH2Cl2=1:2) conduct
Intermediate buffer layer；
(3) top layer is used as dissolved with the methylene chloride (4 mL) of chiral monodentate organic ligand containing N L (0.08 mmol, 20 mg)
It is slowly added in test tube, which blocky clear crystal occurs after standing 4-5 days at room temperature, methanol and washing are used in filtering respectively
Wash, drying at room temperature to get arrive (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]n, calculate
Yield is 86% (calculating by silver).
(-)-is determined using Bruker SMART APEX CCD diffractometer single crystal diffractometer at normal temperature
2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nMolecular structure (see Fig. 1 and Fig. 2).Such as
Shown in Fig. 2, the molecular structure of the chirality silver complex luminescent material is by repetitive unit [Ag (L) ClO4] composition two-dimensional layer
Structure.(-) -2- (4 '-pyridyl group) -4,5- firpene-has been measured using Biologic MS-500 spectropolarimeter
Pyridine chirality silver complex [Ag (L) ClO4]nCircular dichroism (see figure 5), the complex is in wavelength X=253 and 320 nm
The negative Cotton effect of place's display, it was confirmed that the chiral optical activity of the silver complex luminescent material.
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nLuminescent properties test:
Under room temperature, (-) -2- (4 '-pyridyl group) -4 is tested using FLS980P fluorescence spectrometer,
5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nTransmitting and excitation spectrum (respectively corresponding Fig. 3 and 4).Test shows:
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nUnder the ultraviolet light of 370 nm,
The orange-red fluorescence of 600 nm can be emitted.This result shows that: preparation-obtained (-) -2- (4 '-pyridyl group) -4,5- pinane
Alkene-pyridine chirality silver complex [Ag (L) ClO4]nIt is displaced with big Stokes, can effectively absorb ultraviolet light, generate visible light
Transmitting, therefore, the chirality silver complex have efficient light transfer capability, have in terms of the selection of light-switching device and development
Potential application prospect.
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. in the round-bottomed flask of 250 mL, 5.3 grams of 4- second the preparation of 4- (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine will be added in round-bottomed flask, mixture heating with 25 mL pyridinium dissolutions dissolved with 20 mL pyridine solutions of 18 grams of iodine
To 100 DEG C, reacts 4.5 hours, then cool to room temperature and filter, it is secondary with a small amount of pyridine flushing, it is obtained 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 a system
Standby obtained 4.2 grams of 4- (pyridine acetyl group) pyridinium iodide intermediate and 2.5 grams of ammonium acetate (NH4Ac) it is placed in three-neck flask
In, add the formamide (CH of 45 mL3CONH2), it is stirred continuously lower myrte (-)-myrtenal for being added 2.8 grams
(Bellingwell company's production), is heated to 75 DEG C, reacts 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 chiral monodentate organic ligand L:(- containing N) -2- (4 '-pyrroles
Piperidinyl) -4,5- firpene-pyridine.
Yield is that 87%(is calculated by intermediate).Elemental analysis: molecular formula C is pressed17H18N2(molecular weight 250.33): it calculates
Be worth (%): C, 81.56; H, 7.25; N, 11.19;Measured value (%): C, 81.51; H, 7.34; N, 11.13.
Infrared spectroscopy IR (KBr): 2947 (s), 2991 (m), 2864 (v), 1584 (m), 1450 (s), 1383 (m), 782
(m), 756(s)。
Embodiment 2
The present embodiment (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nPreparation side
Method, steps are as follows:
It (1) will be dissolved with AgClO4The methanol solution (4 mL) of (0.04 mmol, 8.3 mg) is seated in the bottom of test tube；
(2) mixed solution (the volume ratio CH of 8mL methanol and methylene chloride is then added3OH : CH2Cl2=1:2) be used as in
Between buffer layer；
(3) top layer is used as dissolved with the methylene chloride (4 mL) of chiral monodentate organic ligand containing N L (0.04 mmol, 10 mg)
It is slowly added in test tube, which blocky clear crystal occurs after standing 4-5 days at room temperature, methanol and washing are used in filtering respectively
Wash, drying at room temperature to get arrive (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]n。
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. in the round-bottomed flask of 250 mL, 5.3 grams of 4- second the preparation of 4- (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine will be added in round-bottomed flask, mixture heating with 30 mL pyridinium dissolutions dissolved with 25 mL pyridine solutions of 21 grams of iodine
To 110 DEG C, reacts 4.5 hours, then cool to room temperature and filter, it is secondary with a small amount of pyridine flushing, it is obtained 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 a system
Standby obtained 4.2 grams of 4- (pyridine acetyl group) pyridinium iodide intermediate and 3.2 grams of ammonium acetate (NH4Ac) it is placed in three-neck flask
In, add the formamide (CH of 50 mL3CONH2), it is stirred continuously lower myrte (-)-myrtenal for being added 2.8 grams
(Bellingwell company's production), is heated to 85 DEG C, reacts 12 hours under nitrogen, Off-white solid is obtained by filtration in above-mentioned product, and
It is rinsed with water, it is then that solid is dry with ethyl alcohol recrystallization, obtain chiral monodentate organic ligand L:(- containing N) -2- (4 '-pyridines
Base) -4,5- firpene-pyridine.
Embodiment 3
The present embodiment (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]nPreparation side
Method, steps are as follows:
It (1) will be dissolved with AgClO4The methanol solution (7 mL) of (0.08 mmol, 16.6 mg) is seated in the bottom of test tube；
(2) mixed solution (the volume ratio CH of 9 mL methanol and methylene chloride is then added3OH : CH2Cl2=1:2) conduct
Intermediate buffer layer；
(3) top layer is used as dissolved with the methylene chloride (6 mL) of chiral monodentate organic ligand containing N L (0.08 mmol, 20 mg)
It is slowly added in test tube, which blocky clear crystal occurs after standing 4-5 days at room temperature, methanol and washing are used in filtering respectively
Wash, drying at room temperature to get arrive (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]n。
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. in the round-bottomed flask of 250 mL, 5.3 grams of 4- second the preparation of 4- (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine will be added in round-bottomed flask, mixture heating with 28 mL pyridinium dissolutions dissolved with 24 mL pyridine solutions of 20 grams of iodine
To 105 DEG C, reacts 4.5 hours, then cool to room temperature and filter, it is secondary with a small amount of pyridine flushing, it is obtained 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 a system
Standby obtained 4.2 grams of 4- (pyridine acetyl group) pyridinium iodide intermediate and 3.0 grams of ammonium acetate (NH4Ac) it is placed in three-neck flask
In, add the formamide (CH of 48 mL3CONH2), it is stirred continuously lower myrte (-)-myrtenal for being added 2.8 grams
(Bellingwell company's production), is heated to 80 DEG C, reacts 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 chiral monodentate organic ligand L:(- containing N) -2- (4 '-pyrroles
Piperidinyl) -4,5- firpene-pyridine.
Claims (5)
1. one kind (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex, (-) -2- (4 '-pyridyl group) -
4,5- firpene-pyridine chirality silver complex molecular formula is [Ag (L) ClO4]∞, wherein L is chiral monodentate organic ligand containing N:
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine, structural formula are。
2. the preparation side of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex according to claim 1
Method, it is characterised in that: steps are as follows:
It (1) will be dissolved with AgClO4Methanol solution be put into test tube as bottom, wherein the concentration of silver perchlorate is 0.01 ~ 0.02
mol/L；
(2) mixed solution of methanol and methylene chloride is added on bottom as intermediate buffer layer；
(3) will be dissolved with chiral monodentate organic ligand L:(- containing N) -2- (4 '-pyridyl group) -4,5- firpene-pyridine methylene chloride is molten
Liquid is slowly added in test tube as top layer, and wherein the concentration of chiral monodentate organic ligand containing N L is 0.01 ~ 0.02 mol/L；It should
There is blocky clear crystal in test tube after standing 4-5 days at room temperature, methanol and water washing are used in filtering respectively, and drying at room temperature obtains
(-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex [Ag (L) ClO4]∞；
The bottom, intermediate buffer layer and the liquid volume of top layer ratio are (4 ~ 7): (6 ~ 9): (4 ~ 7).
3. the preparation side of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex according to claim 2
Method, it is characterised in that: the volume ratio of methanol and methylene chloride is in the mixed solution of methanol and methylene chloride in the step (2)
1:2。
4. the preparation side of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex according to claim 2
Method, it is characterised in that: the AgClO4It is 1:1 with the ratio between the amount of substance of chiral monodentate organic ligand containing N L.
5. the preparation side of (-) -2- (4 '-pyridyl group) -4,5- firpene-pyridine chirality silver complex according to claim 1
Method, it is characterised in that: chiral monodentate organic ligand L:(- containing N in the step (3)) -2- (4 '-pyridyl group) -4,5- firpene-pyrrole
Pyridine the preparation method is as follows:
A. in the round-bottomed flask of 250 mL, 5.3 grams of 4- second the preparation of 4- (pyridine acetyl group) pyridinium iodide intermediate: are added
Acyl pyridine will be added in round-bottomed flask with 25 ~ 30 mL pyridinium dissolutions dissolved with 20 ~ 25 mL pyridine solutions of 18 ~ 21 grams of iodine,
Mixture is heated to 100 ~ 110 DEG C, reacts 4 ~ 4.5 hours, then cools to room temperature and filter, and rinses two with a small amount of pyridine
It is secondary, intermediate needed for gray solid is is obtained after vacuum drying；
B. chiral monodentate organic ligand L:(- containing N) synthesis of -2- (4 '-pyridyl group) -4,5- firpene-pyridine: weigh step a system
Standby obtained 4.2 grams of 4- (pyridine acetyl group) pyridinium iodide intermediate and 2.5 ~ 3.2 grams of ammonium acetates are placed in three-neck flask, then
The formamide of 45 ~ 50 mL is added, is stirred continuously lower myrte (-)-myrtenal for being added 2.8 grams, is heated to 75-85
DEG C, it is reacted 12-12.5 hours under nitrogen, Off-white solid is obtained by filtration in above-mentioned product, and be rinsed with water, tied again with ethyl alcohol
Then solid is dried in vacuo to obtain chiral monodentate organic ligand containing N L by crystalline substance.
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