CN104230965B - The preparation of ring-type silver complex and the application in identification object thereof - Google Patents
The preparation of ring-type silver complex and the application in identification object thereof Download PDFInfo
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- CN104230965B CN104230965B CN201410448140.5A CN201410448140A CN104230965B CN 104230965 B CN104230965 B CN 104230965B CN 201410448140 A CN201410448140 A CN 201410448140A CN 104230965 B CN104230965 B CN 104230965B
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- silver complex
- naphthalene
- imidazole
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- alkoxy
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Abstract
<b> the invention discloses the single crystal data of N-heterocyclic carbine metal silver complex.Nitrogen heterocyclic carving preparation methods of silver metal complexes is in organic solvent & lt;/ b>& lt;B>2, 3 - & lt;/ b>& lt;B>2 & lt;/ b>& lt;B>(2 & lt; / b> & lt; b> '& lt; / b> & lt; b> - & lt; / b> & lt; b> halogen alkoxy & lt; / b> & lt; b>)& lt;/ b>& lt;B>Naphthalene and & lt;/ b>& lt;B>N - & lt;/ b>& lt;B>Substituent benzene and imidazole reaction, the products for & lt;/ b>& lt;B>2 & lt;/ b>& lt;B>, & lt;/ b>& lt;B>3 - & lt;/ b>& lt;B>2 & lt;/ b>& lt;B>[2 & lt; / b> & lt; b> '& lt; / b> & lt; b> - & lt; / b> & lt; b> (& lt; / b> & lt; b> N - & lt; / b> & lt; b> substituent benzene and imidazole) alkoxy & lt; / b> & lt; b>]& lt;/ b>& lt;B>Naphthalene halide, and exchange in the methanol into six fluoride phosphate;Under inert gas protection, will & lt;/ b>& lt;B>2 & lt;/ b>& lt;B>, & lt;/ b>& lt;B>3 - & lt;/ b>& lt;B>2 & lt;/ b>& lt;B>[2 & lt; / b> & lt; b> '& lt; / b> & lt; b> - & lt; / b> & lt; b> (& lt; / b> & lt; b> N - & lt; / b> & lt; b> substituent benzene and imidazole) alkoxy & lt; / b> & lt; b>]& lt;/ b>& lt;B>Naphthalene six fluoride phosphate and metal compounds in high purity water reagent reaction in the preparation of carving metal complexes.The N-heterocyclic carbine metal silver complex proposed be a kind of in normal conditions can the senior fluorescent material of stable existence, there is adjustable structure, prepare succinct, the obvious advantage of fluorescence photosensitive effect, can, as acceptor in fluorescence molecule identification system, be expected to be applied in molecular recognition field.</b>
Description
About the statement subsidizing research or exploitation
The present invention is state natural sciences fund (fund number is 21172172), and Tianjin Natural Science Fund In The Light (fund number is 11JCZDJC22000) and Tianjin innovation team of institution of higher education training plan (fund number is TD12-5038) are carried out under subsidizing.
Technical field
The invention belongs to Organometallic Chemistry technical field, relate to N-heterocyclic carbine metal silver complex as the applied research of acceptor in molecular recognition field.
Background technology
N-heterocyclic carbine is due to its higher molecular orbital energy, and result in its low stability, this reason hinders the development of carbene chemistry at first.But along with development that is theoretical and laboratory apparatus, the research for N-heterocyclic carbine chemistry achieves great successes in recent years.First Skell takes to the laboratory study of Cabbeen the fifties in eighties of last century.1964, Cabbeen was introduced in inorganic and vitochemical research field, and this is that the follow-up study of Cabbeen opens new chapter.Last century, early sixties Wanzlick and Ofele studied thiazole-2-carbene as a kind of important organic reaction intermediate, find that the electron donation of two ortho position nitrogen-atoms in imidazole ring can help the carbene center that stable 2-position carbon is formed, investigator afterwards proves that this stabilization is actually and is caused by the delocalization of electronics and conjugation.Although the work of Wanzlick does not obtain the N-heterocycle carbine dissociated, their research is that basis that is theoretical and experiment has been established in the development of N-heterocyclic carbine chemistry afterwards.
The research of N-heterocyclic carbine metal title complex now one of Disciplinary Frontiers becoming Organometallic Chemistry.By theorize scholar and Organometallic scholar to N-heterocyclic carbine Quality Research, although find that it is similar to the Phosphine ligands of electron rich, it has better thermostability, water tolerance, air stability, the advantages such as lower toxicity and homogeneous reaction immobilization.In addition, in recent years, the application of fluorescent probe enjoys the concern of people, because metal ion match not only as having the fluorophore postponing to launch, can also be used as acceptor, also can play dual function simultaneously.N-heterocyclic carbine more and more causes the attention of people because of the performance of its uniqueness, and is applied to the research field of Organometallic Chemistry.
Summary of the invention
The present invention proposes the application in molecular recognition field using N-heterocyclic carbine metal silver complex as acceptor.For completing foregoing invention object, technical solution of the present invention is as follows:
N-heterocyclic carbine metal silver complex is from the compound of following formula subrepresentation:
Adopting of N-heterocyclic carbine metal silver complex of the present invention obtains in the following method:
It is characterized in that:
(1) in organic solvent with different substituents group and C
1-C
6halogenated alkane and benzoglyoxaline react, and products therefrom reacts generation 2,3-bis-[2 '-(N-substituting group benzoglyoxaline) alkoxyl group] naphthalenesulfonyl halide again with 2,3-bis-(2 '-halogen alkoxyl group) naphthalene.And be hexafluoro-phosphate radical negative ion by halogen ion-exchange in methyl alcohol.
(2) under protection of inert gas; by 2; 3-bis-[2 '-(N-substituting group benzoglyoxaline) alkoxyl group] naphthalene hexafluorophosphate metallizing thing is that the ratio of 0.5-3 ~ 2-5mol joins in flask with mol ratio; after the high-purity organic molten agent dissolves dewatered; react 12 ~ 24 hours at 0C ~ 100C temperature; filter not tolerant, volatilization or ether diffusion obtain carbine metal title complex naturally.
Wherein said substituted benzimidazole is ethyl benzo imidazole, n-propyl benzoglyoxaline, normal-butyl benzoglyoxaline, sec-butyl benzoglyoxaline.1-picolyl benzoglyoxaline, naphthalene benzoglyoxaline, anthracene benzoglyoxaline or benzyl benzimidazole.Substituted benzimidazole of the present invention.Preferred ethyl benzo imidazole, n-propyl benzoglyoxaline, normal-butyl benzoglyoxaline, 1-picolyl benzoglyoxaline.
Wherein said metallic compound is selected from silver suboxide, Silver monoacetate, silver carbonate, Glacial acetic acid mercury, mercury halide, mercuric bromide, iodate tribute cuprous halide, Red copper oxide, Quilonum Retard, nickel acetate, nickelous chloride.The mixture of one or more of Cu Suan Palladium, zirconium white, yttrium oxide, lanthanum trioxide, Palladous chloride, acetonitrile palladium chloride.Be more preferably silver suboxide, Glacial acetic acid mercury, mercury chloride, mercuric bromide, red mercury iodide or Palladous chloride.
Wherein, halogen is selected from fluorine, chlorine, bromine, iodine, hexafluoro-phosphate radical negative ion etc.Be preferably as hexafluoro-phosphate radical negative ion.
Described organic solvent is selected from the mixture of one or more in methyl alcohol, tetrahydrofuran (THF), methylene dichloride, trichloromethane, 1,2-ethylene dichloride, acetone, ether, acetonitrile, nitroethane, DMF, dimethyl sulfoxide (DMSO).Preferred acetone, tetrahydrofuran (THF) (THF), methyl alcohol in feature (1).The mixture of one or more in feature (2) in preferred acetonitrile, methylene dichloride, DMF, dimethyl sulfoxide (DMSO).
N-heterocyclic carbine metal crown ether of the present invention, is characterized in that the single crystal data of N-heterocyclic carbine metal silver complex is as follows:
Experiment proves:
N-heterocyclic carbine metal silver complex, under 25C, adds LiNO in ethanolic soln respectively
3, NaNO
3, KNO
3, NH
4nO
3, AgNO
3, Ca (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, Cd (NO
3)
2, Al (NO
3)
3after, measure its fluorescent absorption.Selective absorber peak reduces maximum Al (NO
3)
3carry out titration.By N-heterocyclic carbine metal silver complex as acceptor, add with microsyringe the Al (NO that concentration increases gradually wherein
3)
3solution (1 × 10
-5mol/L).Solution has strong absorption at 325nm place.After each interpolation, within 8-10 minute, reach molecular balance and just can record corresponding fluorescent absorption intensity, its fluorescent absorption intensity is weakened gradually.See accompanying drawing 2 and 3.
The preparation method of N-heterocyclic carbine metal silver complex crystal of the present invention, it is characterized in that gained title complex 1(0.010g, 0.0139mmol) be dissolved in 5mL1, in 2-ethylene dichloride/DMSO (v:v=2:1), under this solution being placed in 25 DEG C of conditions, and slowly spread by ether, the yellow transparent bulk crystals of applicable X-ray single crystal diffraction test is grown after one week at test tube wall.
N-heterocyclic carbine metal silver complex of the present invention is identifying the application in molecule object as acceptor.Wherein said molecule object comprises: LiNO
3, NaNO
3, KNO
3, NH
4nO
3, AgNO
3, Ca (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, Cd (NO
3)
2, Al (NO
3)
3.
N-heterocyclic carbine metal silver complex proposed by the invention be a kind of in normal conditions can the senior fluorescent material of stable existence, there is adjustable structure, prepare succinct, the obvious advantage of fluorescence photosensitive effect, can as acceptor in fluorescence molecule identification system, be expected to be applied in molecular recognition field, detailed in Example 2 and embodiment 3.
Accompanying drawing illustrates:
Fig. 1 is the crystalline structure figure containing silver complex (embodiment 5);
Fig. 2, for containing silver complex (embodiment 5) under 25C, adds LiNO in ethanolic soln respectively
3, NaNO
3, KNO
3, NH
4nO
3, AgNO
3, Ca (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, Cd (NO
3)
2, Al (NO
3)
3after fluorescence spectrum figure;
Fig. 3, for containing silver complex under 25C, adds the Al (NO of different concns in ethanolic soln
3)
3after fluorometric titration spectrogram;
Fig. 4, for containing silver complex under 25C, adds the Al (NO of different concns in ethanolic soln
3)
3after uv absorption spectra.
Specific embodiments:
Below in conjunction with preferred embodiment, the present invention will be further described, be illustrated especially, prepare the initial substance of the compounds of this invention, halogenated alkane, salt of wormwood, sodium borohydride, anhydrous magnesium sulfate, sulfur oxychloride, ammonium hexafluorophosphate etc. and all can commercially or easily be obtained by known method.
The reagent prepared used by the compounds of this invention all derives from Tianjin Ke Wei Chemical Co., Ltd., and rank is analytical pure.
Need in addition to be illustrated: all experimental implementation use Schlenk technology, and solvent is through normal process purifying.All for the synthesis of being all analytical pure with the reagent analyzed, not through further process.Fusing point is measured by Boetius block apparatus.
1hNRM composes by mercury variable V x400 spectrophotometer record, surveying range: 400MHz.Chemical shift, δ, the TMS with reference to international standard measures.Fluorescence spectrum is by CaryEclipse fluorescent spectrophotometer assay.UV spectrum is measured by JASCO-V570 infrared spectrophotometer.
Embodiment 1
By N-heterocyclic carbine metal silver complex (embodiment 5) (1 × 10
-5mol/L) join in ethanolic soln under 25C, add the LiNO of 30 times of concentration wherein respectively
3, NaNO
3, KNO
3, NH
4nO
3, AgNO
3, Ca (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, Cd (NO
3)
2, Al (NO
3)
3its fluorescent absorption of rear mensuration.After each interpolation, within 8-10 minute, reach molecular balance and just can note down corresponding fluorescence intensity.Find when adding LiNO
3, NaNO
3, KNO
3, NH
4nO
3, AgNO
3, Ca (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, Cd (NO
3)
2time on its fluorescence intensity almost without impact, and when adding Al
3+fluorescence intensity significantly decreases.Selective absorber peak reduces maximum Al
3+fluorescence and ultraviolet performance measurement are carried out to acceptor.See accompanying drawing 2 and 3.
Embodiment 2
Fluorometric titration is measured by the quartz cell of 1cm path length by CaryEclipse spectrophotofluorometer.The ethanol used in titration to dewater the dehydrated alcohol obtained with sodium.The carrying out of titration is by acceptor (embodiment 5) (1 × 10
-5mol/L) add in the cuvette of 4mL, and add with microsyringe the Al that concentration increases gradually
3+(0.0-70.0 × 10
-5mol/L).After each interpolation, after within 8-10 minute, reaching molecular balance, just can note down corresponding fluorescence intensity.Strong peak is had at 325nm place, and along with Al
3+the increase fluorescence intensity of ionic concn reduces gradually until no longer change.This illustrates Al
3+it is the quencher of acceptor.Data analysis uses Origin8.0.See accompanying drawing 3.
Embodiment 3
Ultraviolet titration is measured with the quartz colorimetric utensil of 1cm path length by JASCO-V570 spectrophotometer.The ethanol used in titration to dewater the dehydrated alcohol obtained with sodium.The carrying out of titration is by acceptor (embodiment 5) (6.0 × 10
-5mol/L) add in the cuvette of 4mL, and add with microsyringe the Al that concentration increases gradually
3+(0.0-6.0 × 10
-5mol/L).After each interpolation, within 8-10 minute, reach molecular balance and just can note down corresponding fluorescence intensity.Uv-absorbing increases gradually along with the increase of iodide ion concentration, makes working curve (see accompanying drawing 4 illustration), known Al by the point choosing 205nm place on every bar ultraviolet curve
3+to be combined at 1: 1 with acceptor.Data analysis uses Origin8.0.See accompanying drawing 4.
Embodiment 4
Benzoglyoxaline (1.000g will be dissolved with, tetrahydrofuran (THF) 8.5mmol) joins and is dissolved with sodium hydride (0.244g, in tetrahydrofuran (THF) (25mL) 10.2mmol), mixed solution heats 1h at 60 DEG C, bromination of n-butane (1.145g will be dissolved with, tetrahydrofuran (THF) (20mL) 9.3mmol) is added dropwise in above-mentioned mixing solutions, at 60 DEG C, heat 48h.Yellow solution is spin-dried for, washes with water and be spin-dried for thing.And with dichloromethane extraction, organic phase anhydrous magnesium sulfate drying, suction filtration obtains yellow liquid 1-normal-butyl-benzoglyoxaline, output: 1.221g (90%).
2,3-dihydroxy naphthlene diphenol (10.000g, 62.5mmol) is dissolved in 150mLDMF, in solution, adds anhydrous K
2cO
3(34.552g, 250.0mmol), at N
2under protection; heating 60C stirs 0.5h; ethylene chlorhydrin (20.000g is dripped in this mixed solution; 250.0mmol); and be warming up to 110 DEG C, heated and stirred 24h at this temperature, reaction gained liquid is poured in 500mL water; obtain white precipitate and be product 2,3-bis-(2 '-hydroxyethyl) naphthalene.Productive rate 13.965g (90%), fusing point: 132-134 DEG C.
16
δ3.82(t,
J=5.0Hz,4H,C
H 2),4.13(t,
J=5.2Hz,4H,C
H 2),4.97(d,
J=2.0Hz,2H,O
H),7.32(m,4H,Ph
H),7.73(q,
J=4.0Hz,2H,Ph
H).
13CNMR(100MHz,DMSO-d
6):
δ148.7(Ph
C),128.8(Ph
C),126.1(Ph
C),123.8(Ph
C),107.7(Ph
C),70.0(O
CH
2CH
2),59.3(OCH
2 CH
2).
Under room temperature condition, by thionyl chloride (23.972g, 201.5mmol) in one hour, slowly instillation is dissolved with 2,3-bis-(2 '-hydroxyethyl) naphthalene (10.000g, 40.3mmol) with pyridine (15.938g, chloroformic solution (100mL) 201.5mmol), stirs 12h by mixed solution at 60C.Reaction solution is poured in 300mL water, and by chloroform (30mL × 3) aqueous layer extracted, extraction liquid and organic layer merge, and use anhydrous MgSO
4drying, revolves and steams buff powder is product 2,3-bis-(2 '-halogen alkoxyl group) naphthalene.Productive rate 6.442g (56%), fusing point: 72-74 DEG C.
13
δ3.92(t,
J=6.0Hz,4H,C
H 2),4.40(t,
J=18.4Hz,4H,C
H 2),7.20(s,2H,Ph
H),7.37(m,2H,Ph
H),7.69(m,2H,Ph
H).
13CNMR(100MHz,CDCl
3):
δ148.4(Ph
C),129.6(Ph
C),126.4(Ph
C),124.7(Ph
C),110.2(Ph
C),69.3(O
CH
2CH
2),41.7(OCH
2 CH
2)。
N-normal-butyl benzoglyoxaline (2.619g is added in tetrahydrofuran solvent, 21.1mmol), NaI (3.164g, 21.1mmol) He 2,3-bis-(2 '-halogen alkoxyl group) naphthalene (2.000g, 7.0mmol), under reflux conditions heated and stirred 7 days, obtain yellow oil and be 2,3-bis-[2 '-(N-normal-butyl benzoglyoxaline) alkoxyl group] naphthalene iodide.Ammonium hexafluorophosphate and obtained above 2 are added in methyl alcohol, 3-bis-[2 '-(N-normal-butyl benzoglyoxaline) alkoxyl group] naphthalene iodide, stirring at normal temperature 3 days, generate white mass, suction filtration obtains product, and washing a small amount of methyl alcohol with water, drying obtains product 2,3-bis-[2 '-(N-substituting group benzoglyoxaline) alkoxyl group] naphthalene hexafluorophosphate (L
1h
2).Productive rate: 4.212g (80%).Fusing point: 112-114 DEG C.
16
δ0.88(t,
J=7.4Hz,6H,C
H 3),1.27(m,4H,C
H 2),1.78(m,4H,C
H 2),4.21(t,
J=7.0Hz,4H,C
H 2),4.50(t,
J=5Hz,4H,C
H 2),4.69(t,
J=4.6Hz,4H,C
H 2),7.36(t,
J=3.6Hz,4H,Ph
H),7.74(q,
J=3.2Hz,2H,Ph
H),7.80(d,
J=1.6Hz,2H,imi
H),7.81(d,
J=1.6Hz,2H,imi
H),9.25(s,2H,2-imi
H)。
Embodiment 5
Silver suboxide (0.092g, 0.4mmol) is added and is dissolved with part (L
1h
2) (0.170g, 0.2mmol) 1,2-ethylene dichloride/DMSO (15mL, v:v=2:1) solution in, this suspension is stirred 24h under 40 DEG C of conditions.After filtration, solution is concentrated into 5mL, adds 5mL ether and occur white powder, filter and obtain title complex 1.Productive rate: 0.048g (30%), fusing point: 248-250 DEG C.
364064216
δ0.92(t,
J=11.4Hz,6H,C
H 3),1.44(m,4H,C
H 2),1.93(m,4H,C
H 2),4.40(t,
J=4.2Hz,4H,C
H 2),4.64(t,
J=6.8Hz,4H,C
H 2),5.14(t,
J=4.0Hz,4H,C
H 2),7.23(s,2H,Ph
H),7.30(q,
J=3.2Hz,2H,Ph
H),7.55(m,4H,Ph
H),7.67(q,
J=3.2Hz,2H,Ph
H),7.90(t,
J=4.4Hz,2H,Ph
H),7.99(t,
J=4.2Hz,2H,Ph
H)。
Embodiment 6
The preparation method of N-heterocyclic carbine metal silver complex monocrystalline is as follows: by gained title complex 1(0.010g, 0.0139mmol) be dissolved in 5mL1, in 2-ethylene dichloride/DMSO (v:v=2:1), under this solution being placed in 25 DEG C of conditions, and slowly spread by ether, the yellow transparent bulk crystals of applicable X-ray single crystal diffraction test is grown after one week at test tube wall.
The experiment flow of above-described embodiment 4 and embodiment 5 is as follows:
In sum, content of the present invention is not limited in instances, and the knowledgeable people in same area can propose other example easily within technical director's thought of the present invention, but this example all comprises within the scope of the present invention.
Claims (1)
1. N-heterocyclic carbine metal silver complex is identifying Al (NO as acceptor
3)
3the application of molecule object aspect; The single crystal data of wherein said N-heterocyclic carbine metal silver complex is as follows:
Its compound represented is as follows:
。
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| CN101333225A (en) * | 2008-07-03 | 2008-12-31 | 天津师范大学 | Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications |
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| CN101323624A (en) * | 2008-04-11 | 2008-12-17 | 天津师范大学 | Nitrogen heterocyclic ring double carbine metal complex , preparation and use thereof |
| CN101307065A (en) * | 2008-07-03 | 2008-11-19 | 天津师范大学 | N-heterocyclic dicarbene metal complex connected with ether chain, method for preparing same and use |
| CN101333225A (en) * | 2008-07-03 | 2008-12-31 | 天津师范大学 | Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications |
| CN102219797A (en) * | 2011-04-25 | 2011-10-19 | 天津师范大学 | N-heterocyclic carbene annular metal complexes, preparation method and purpose thereof |
| CN102584864A (en) * | 2012-01-12 | 2012-07-18 | 天津师范大学 | Azacyclo-carbene metal crown ether and application of azacyclo-carbene metal crown ether to identification of objects |
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