CN102219797B - N-heterocyclic carbene annular metal complexes, preparation method and purpose thereof - Google Patents
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- CN102219797B CN102219797B CN201110102622.1A CN201110102622A CN102219797B CN 102219797 B CN102219797 B CN 102219797B CN 201110102622 A CN201110102622 A CN 201110102622A CN 102219797 B CN102219797 B CN 102219797B
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Abstract
The invention discloses N-heterocyclic carbene annular metal complexes with 1,5-di[1-substituent-3 imidazole ethyl] naphthol diether and 1,4-di[1-substituent-3 benzimidazole ethyl]diphenyl ether as precursors and the preparation method thereof. R in the N-heterocyclic carbene is independent or is combined with other elements to form hydrogen or C1_C6 organic radical, wherein the C1_C6 organic radical contains one or more selected from the group consisting of alkyl group, branched alkyl group, naphthenic base, cycloalkenyl group, alkynyl, aryl group, arylalkyl, heterocycle, alkoxy and substitution derivatives of alkoxy. The N-heterocyclic carbene annular metal complexes provided by the invention are mainly applied in the technical field of fluorescent agents.
Description
about subsidizing the statement of research or exploitation
the present invention carries out under the subsidy of state natural sciences fund (fund number is 20872111) and Tianjin Natural Science Fund In The Light (fund number is 11JCZDJC22000).
Technical field
the invention belongs to organic synthesis and Organometallic Chemistry technical field, relate to the synthetic of N-heterocyclic carbine annular metal title complex, in particular containing 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and Isosorbide-5-Nitrae-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether are as preparation method and the application of the N-heterocyclic carbine annular metal title complex of precursor.
Background technology
organometallic Chemistry is one of emphasis problem of current chemical field research, and they have not only driven the progress of novel method for synthesizing, have more driven renewal and the development of novel material.Metal carbene title complex is one of Disciplinary Frontiers of Organometallic Chemistry research.Arduengo in 1991 for the first time separated obtained stable free N-heterocycle carbine (NHC) after, the research of N-heterocycle carbine metal complexes has obtained development rapidly at recent two decades.N-heterocycle carbine is higher than the bond energy of corresponding organic phosphine with the bond energy that metal carries out coordination, and the advantage that they demonstrate than organophosphite ligand compound is mainly that to come from its stability to high temperature, humidity and oxygenant higher.From its Application Areas, N-heterocycle carbine metal complexes is a kind of novel catalyzer with high reactivity, highly selective, in homogeneous catalytic reaction, has a good application prospect.In addition, N-heterocycle carbine metal complexes also can be applied to the fields such as material science and photochemistry etc.The role in fluorescent molecule switch that comprises metal ion match recent years has received scientist's very big concern, because metal ion match both can also can be used as acceptor as having the fluorophore that postpones transmitting, also can serve a dual purpose simultaneously.Role in fluorescent molecule switch great majority are structures of " fluorophore-interstitial-acceptor " type, or several so identical part or the combination of distinct portions.Metal complexes has its unique distinction as the assembly of role in fluorescent molecule switch, has the features such as highly sensitive, simple, reliable.Along with the expansion of the deep and research range of studying, N-heterocycle carbine metal complexes will be applied in fields such as chemistry subject, life science, environmental analysis and clinical medicine as the motif compound of fluorescent switch.
Summary of the invention
the object of the present invention is to provide by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and 1,4-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether is as the N-heterocyclic carbine annular metal title complex of precursor, particularly by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and Isosorbide-5-Nitrae-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether are as the cyclic complex of the nitrogen heterocyclic carbene silver of precursor.
the present invention also relates to nitrogen heterocyclic carbene silver cyclic complex and preparation method thereof.
the present invention relates to this type of metal-organic hydrogen spectrum demarcates.
the present invention relates to the method for forming of the crystal of this type of metallorganics, the research of take off data and data.
the organic cyclic complex of metal involved in the present invention is all that the method cultivation by spreading or volatilizing obtains.
the organic cyclic complex of metal involved in the present invention has all carried out the mensuration of nuclear magnetic data sign and fluorescence data.
the present invention further provides the method for preparing N-heterocyclic carbine annular metal title complex under protection of inert gas, and it has been carried out to crystallography sign.
a metal-organic complex in the present invention is all measured and data characterization by x-ray diffractometer.
the present invention has further related to by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and Isosorbide-5-Nitrae-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether and has been mainly used in fluorescent agent technical field as the N-heterocyclic carbine annular metal title complex of precursor.
for completing above-mentioned every goal of the invention, technical solution of the present invention is as follows:
have by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether (1) and Isosorbide-5-Nitrae-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether (2) as the N-heterocyclic carbine annular metal title complex (I) of precursor and (II):
（
1）
（
2）
（
I）
（
II）
wherein, R is independently or combines for hydrogen or C
1
-C
6
organic radical, C
1
-C
6
organic radical comprises alkyl, branched-chain alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, aryl, arylalkyl, nitrogen heterocyclic ring or alkoxyl group.
for the metallic cation of silver or palladium, m is 1-4;
x
-
halogen anion or hexafluoro-phosphate radical negative ion.
wherein, C
1
-C
6
organic radical is selected from alkyl, for example C
2
h
5
, C
6
h
13
; Branched-chain alkyl is isobutyl-, normal-butyl or neo-pentyl for example; Cycloalkyl is cyclopropane methyl or tetramethylene ethyl for example; Alkenyl is vinyl, propenyl or allyl group for example; Cycloalkenyl group is cyclopropenyl radical for example; Alkynyl is ethynyl for example; Aryl is benzyl, menaphthyl, anthracene methyl for example; Nitrogen heterocyclic ring and substitutive derivative thereof, for example ethyl imidazol(e), normal-butyl imidazoles, benzyl imidazole, ethyl benzo imidazole, normal-butyl benzo imidazoles or 1-picolyl benzoglyoxaline.
halogen is selected from chlorine, bromine, iodine, preferably iodide ion.
the preparation method who the invention discloses N-heterocyclic carbine annular metal title complex, is characterized in that:
under protection of inert gas; will be by 1; 5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and 1; 4-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether be take as the N-heterocyclic carbine salt of precursor and metallic compound the ratio that mol ratio is 0.5-3～2-6 and is joined in reaction vessels; after dissolving with the high-purity organic solvent dewatering, at 0 ℃～100 ℃ temperature, react 12～24 hours, filter; naturally volatilization, obtains Cabbeen annular metal title complex.
metallic compound of the present invention is selected from wherein a kind of in silver suboxide, Silver monoacetate, silver carbonate, Glacial acetic acid mercury, mercury halide, cuprous halide, cuprous iodide, Red copper oxide, Quilonum Retard, nickel acetate, Cu Suan Palladium, Palladous chloride, acetonitrile Palladous chloride.Preferred Silver monoacetate, silver carbonate, mercury halide, Red copper oxide, nickel acetate, Cu Suan Palladium, zirconium white, Palladous chloride or acetonitrile Palladous chloride.Be more preferably silver suboxide, Glacial acetic acid mercury or acetonitrile Palladous chloride.
organic solvent of the present invention is selected from tetrahydrofuran (THF) (THF), methylene dichloride, trichloromethane, 1, any one or its mixture in 2-ethylene dichloride, acetone, ether, acetonitrile, nitroethane, DMF, dimethyl sulfoxide (DMSO).Preferred acetone, 1,2-ethylene dichloride, DMF or dimethyl sulfoxide (DMSO), be more preferably tetrahydrofuran (THF) (THF), methylene dichloride or acetonitrile.Wherein mixed solvent is the mixing solutions of THF and methylene dichloride.
n-heterocyclic carbine annular metal title complex of the present invention, wherein typical metal complexes is as follows:
the invention discloses by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and Isosorbide-5-Nitrae-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether as the N-heterocyclic carbine annular metal title complex of precursor in the application aspect fluorescent agent.
the molecular formula of the typical nitrogen heterocyclic carbene silver cyclic complex of the present invention is C
48
h
56
ag
2
f
12
n
8
o
4
p
2
.
the molecular formula of another nitrogen heterocyclic carbene silver cyclic complex is C
64
h
76
ag
2
f
12
n
8
o
4
p
2
, what be illustrated especially is as follows as the cyclic complex monocrystalline data of the nitrogen heterocyclic carbene silver of precursor by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and Isosorbide-5-Nitrae-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether:
crystal data and structure refinement parameter are included in supportive information.On Bruker SMART 1000 CCD diffractometers, carry out, experimental temperature is 113 (2) K, under 50kV and 20mA, with Mo-Ka radiation (0.71073), operate, with SMART and SAINT software, carry out data gathering and reduction, the scope of q is 1.8 < q < 25o.Application SADABS program is carried out experience and is absorbed rectification.Crystalline structure is solved by direct method, with SHELXTL bag, whole non-hydrogen atom coordinate anisotropy thermal parameters is carried out to complete matrix least-squares refinement.
in the present invention, disclosed N-heterocyclic carbine metal title complex is relation arranged side by side, without dividing of preferential primary and secondary.
the present invention further discloses by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and Isosorbide-5-Nitrae-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether and be mainly used in fluorescent agent technical field as the N-heterocyclic carbine annular metal title complex of precursor.
experimental results show that: by 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and 1,4-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether is stronger than corresponding part as the fluorescent emission intensity of the N-heterocyclic carbine annular metal title complex of precursor, and change in fluorescence is obvious.At 298K, acetonitrile (1 * 10
-5
mol/L) in solution, excitation wavelength is under 232nm condition, and Ursol D is shown in Figure of description 3 and 4 with the fluorescent quenching figure that it carries out molecular recognition.
what the present invention proposed passes through 1,5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and 1,4-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether is a kind of senior fluorescent material that can stable existence under standard state as the N-heterocyclic carbine annular metal title complex of precursor, there is structure capable of regulating, prepare succinct, the obvious advantage of fluorescence photosensitive effect, can be used for making fluorescent material and fluorescence molecule identification system, be expected to be applied in fluorescence chemical field.
accompanying drawing explanation:
fig. 1 is the crystalline structure figure containing silver complex (embodiment 3);
fig. 2 is the crystalline structure figure containing silver complex (embodiment 4);
fig. 3 is the crystal containing silver complex (embodiment 3), at 298K, and acetonitrile (1 * 10
-5
mol/L) in solution, excitation wavelength is under 232nm condition, fluorescent quenching figure;
fig. 4 is the crystal containing silver complex (embodiment 4), at 298K, and acetonitrile (1 * 10
-5
mol/L) in solution, excitation wavelength is under 232nm condition, fluorescent quenching figure.
Embodiment
for simple and object clearly, below appropriate omission the description of known technology, in order to avoid those unnecessary details impact descriptions to the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, be illustrated especially, prepare the initial substance 1 of the compounds of this invention, 5-dihydroxy naphthlene, 1,4-dihydroxy-benzene, glycol dibromide, 1-ethyl imidazol(e), 1-normal-butyl benzo imidazoles etc. all can have been bought or easily by known method, made from the market.
prepare the compounds of this invention reagent used and all derive from Tianjin Yuan Lihe Ke Wei Chemical Co., Ltd., rank is analytical pure.
need to be in addition illustrated: all experimental implementation are used Schlenk technology, solvent is through normal process purifying.All for the synthesis of with the reagent of analyzing be all analytical pure, not through further processing.Fusing point is measured by Boetius block apparatus.
1
h NMR spectrum is by mercury variable V x400 spectrophotometer record, surveying range: 400 MHz.Chemical shift, δ, with reference to the TMS mensuration of international standard.Fluorescence spectrum is measured by Cary Eclipse fluorescence spectrophotometer.
by NaOH (2.997 g, 74.9 mmol) be mixed with the 30 mL aqueous solution and add wherein Tetrabutyl amonium bromide (0.201g, 0.6 mmol), by 1,5-dihydroxy naphthlene (2.000 g, 12.5 mmol) is dissolved in 40 mL1,2-ethylene dibromide, two kinds of solution are mixed, be heated to 80 C and stir 12h.By water layer is carried out to separatory, brown organic layer is separated, by revolving steaming instrument, glycol dibromide is separated, think to add in residual substance the water of 80ml, then use CHCl
3
extract 3 times, use 30ml at every turn, then the solution after extraction is dried with anhydrous magnesium sulfate.Separated trichloromethane afterwards, obtains the light brown powder of 1,5-bis-[2 '-bromotrifluoromethane] naphthalene diether.Productive rate: 2.737 g (59%).Fusing point: 140-142 C.
1
H?NMR?(400?MH
Z,?
DMSO-d
6
):?
δ?3.95?(t,?
J?=?6.5,?4H,?C
H
2
),?4.49?(t,?
J?=?6.5,?4H,?C
H
2
),?7.03?(d,?
J?=?3.8,?2H,?Ph
H),?7.43?(d,?
J?=?3.8,?2H,?Ph
H),?7.80?(d,?
J?=?3.8,?2H,?Ph
H)。
two [2 '-bromotrifluoromethane] naphthalene diether (4.000 g, 10.7 mmol) and 1-ethyl imidazol(e) (2.468 g, 25.7 mmol) tetrahydrofuran solution (150 mL) stirs seven days, separate out faint yellow solid, filter, with tetrahydrofuran (THF) washing, obtain 1 of yellow, 5-bis-[1-ethyl-3 imidazole ethyl] naphthalene diether bromide.Productive rate: 4.542 g (75%).Fusing point: 166-168 C.
in methanol solution, add 1,5-bis-[1-ethyl-3 imidazole ethyl] naphthalene diether bromide (2.000 g, 3.5 mmol), under stirring at room, add NH
4
pF
6
(1.382 g, 8.5 mmol), stir, and separate out yellow mercury oxide.Filter, solid is washed with methyl alcohol, obtains ligand 1,5-bis-[1-ethyl-3 imidazole ethyl] naphthalene diether hexafluorophosphate.Productive rate: 1.810 g (81%).Fusing point: 200-202 C.
1
H?NMR?(400?MH
Z,?
DMSO-d
6
):?
δ?1.42?(t,?
J?=?7.2,?6H,?C
H
3
),?4.25?(q,?
J?=?7.2,?4H,?C
H
2
),?4.47?(t,?
J?=?4.4,?4H,?C
H
2
),?4.75?(t,?
J?=?4.4,?4H,?C
H
2
),?7.04?(d,?
J?=?8.0,?2H,?Ph
H),?7.35?(t,?
J?=?8.0,?2H,?Ph
H),?7.64?(d,?
J?=?8.0,?2H,?Ph
H),?7.83?(s,?2H,?4?or?5-imi
H),?7.95?(s,?2H,?4?or?5-imi
H),?9.38?(s,?2H,?2-imi
H)?(imi?=?imidazole)。
its experiment flow is as shown below:
the preparation of Isosorbide-5-Nitrae-bis-[2 '-bromotrifluoromethane] benzene diether and preparation 1,5-bis-[2 '-bromotrifluoromethane] naphthalene two ether analogs, be just changed to Isosorbide-5-Nitrae-dihydroxy-benzene by 1,5-dihydroxy naphthlene.Productive rate: 3.216 g (55%), fusing point: 102-104 C.
1
H?NMR?(400?MH
Z,?
CDCl
3
):?
δ3.60?(t,?
J?=?6.0,?4H,?C
H
2
),?4.24?(t,?
J?=?6.0,?4H,?C
H
2
),?6.86?(s,?4H,?Ph
H)。
the preparation of two [1-normal-butyl-3 benzoglyoxaline ethyl] benzene diether hexafluorophosphate is similar to preparation 2, be 1,5-bis-[2 '-bromotrifluoromethane] naphthalene diether and 1-ethyl imidazol(e) are changed to Isosorbide-5-Nitrae-bis-[2 '-bromotrifluoromethane] benzene diether and 1-normal-butyl benzo imidazoles, the product obtaining again with NH
4
pF
6
exchange.Productive rate: 1.960 g (82%), fusing point: 218-220 C.
1
H?NMR?(400?MH
Z
,?DMSO-d
6
):?
δ?1.73?(t,?
J?=?5.4,?6H,?C
H
3
),?2.15?(m,?4H,?C
H
2
),?2.19?(m,?6H,?C
H
2
),?4.37?(t,?
J?=?5.6,?4H,?C
H
2
),?4.57?(q,?
J?=?5.4,?2H,?C
H),?4.92?(t,?
J?=?5.6,?4H,?C
H
2
),?6.86?(m,?4H,?Ph
H),?7.70?(m,?4H,?Ph
H),?8.17?(m,?4H,?Ph
H),?9.95?(s,?2H,?benzimiH)?(benzimi?=?benzimidazole)。
its experiment flow is as shown below:
under nitrogen protection, in acetonitrile (30 mL), add 1,5-bis-[1-ethyl-3 imidazole ethyl] naphthalene diether hexafluorophosphate (0.200 g, 0.3 mmol) and silver suboxide (0.096 g, 0.4 mmol), suspension returning 24 hours.By solution filter and be concentrated to 5 mL, add ether (5 mL) to obtain white precipitate, be the ring compound of 1,5-bis-[1-ethyl-3 imidazole ethyl] naphthalene diether silver.Productive rate: 0.078 g (33%).Fusing point: 246-247 C.The method of forming of Function for Organometallic Complex Crystals, specifically refers at room temperature by diffusion ether and enters and obtain in the organic solution of metal complexes.
1
H?NMR?(400?MH
Z,?
DMSO-d
6
):?
δ?1.40?(t,?
J?=?7.2,?12H,?C
H
3
),?4.25?(q,?
J?=?7.2,?8H,?C
H
2
),?4.51?(t,?
J?=?4.4,?8H,?C
H
2
),?4.76?(t,?8H,?C
H
2
),?7.73-7.78?(m,?12H,?Ph
H),?7.84?(d,?4H,?imi
H),?7.94?(d,?
J?=?7.8,?4H,?imi
H).
its experiment flow is as shown below:
crystalline structure is shown in Figure of description 1.
the preparation of this compound, with to prepare compound 5 similar, is just changed to compound 4 by compound 2.Productive rate: 0.170 g (45%).Fusing point: 245-247 C.The method of forming of Function for Organometallic Complex Crystals, specifically refers at room temperature by diffusion ether and enters and obtain in the organic solution of metal complexes.
1
H?NMR?(400?MH
Z,?
DMSO-d
6
):?
δ0.76?(t,?
J?=?5.6,?12H,?C
H
3
),?1.29?(m,?8H,?C
H
2
),?1.84?(m,?8H,?C
H
2
),?4.23?(t,?
J?=?4.2,?8H,?C
H
2
),?4,58?(t,?
J?=?5.6,?8H,?C
H
2
),?4.99?(t,?
J?=?4.2,?8H,?C
H
2
),?6.40?(s,?
J?=?6.4,?8H,?Ph
H),?7.48?(m,?8H,?Ph
H),?7.84?(d,?
J?=?6.4,?4H,?Ph
H),?8.05?(d,?
J?=?6.4,?4H,?Ph
H).?
its experiment flow is as shown below:
crystalline structure is shown in Figure of description 2.
the N-heterocyclic carbine metal silver complex crystal parameters of embodiment 3 and 4 preparations
application example 1
by embodiment 3 and 4 prepared cyclic complex crystal, be made into certain density acetonitrile solution (1 * 10
-5
mol/L).By liquid testing fluorescence, part corresponding to the fluorescence emission spectrum strength ratio of title complex is stronger, and change in fluorescence is obvious.At 298K, acetonitrile (1 * 10
-5
mol/L) in solution, excitation wavelength is under 232nm condition, and Ursol D carries out the fluorescent quenching figure Figure of description 3 and 4 of molecular recognition with it.
in sum, content of the present invention is not confined in example, and the knowledgeable people in same area can propose easily other example within technical director's thought of the present invention, but this example all comprises within the scope of the present invention.
Claims (5)
1. a N-heterocyclic carbine annular metal complex crystal, its structural formula is as follows:
Its N-heterocyclic carbine metal silver complex crystal parameters of measuring by x-ray diffractometer is as follows:
。
2. a method of preparing N-heterocyclic carbine annular metal complex crystal described in claim 1, is characterized in that:
Under protection of inert gas; will be by 1; 5-bis-[1-substituting group-3 imidazole ethyl] naphthalene diether and 1; 4-bis-[1-substituting group-3 benzoglyoxaline ethyl] benzene diether be take as the N-heterocyclic carbine salt of precursor and metallic compound the ratio that mol ratio is 0.5-3:2-6 and is joined in reaction vessels; after dissolving with the high-purity organic solvent dewatering, at 0 ℃～100 ℃ temperature, react 12～24 hours, filter; naturally volatilization, obtains Cabbeen annular metal title complex.
3. the preparation method of N-heterocyclic carbine annular metal complex crystal described in claim 2, wherein said metallic compound is silver suboxide, Silver monoacetate or silver carbonate.
4. the preparation method of N-heterocyclic carbine annular metal complex crystal described in claim 2, wherein said organic solvent is selected from tetrahydrofuran (THF), methylene dichloride, trichloromethane, 1, the mixture of one or more in 2-ethylene dichloride, acetone, ether, acetonitrile, nitroethane, DMF, dimethyl sulfoxide (DMSO).
Described in claim 1 N-heterocyclic carbine annular metal complex crystal in the application of preparing aspect fluorescent agent material.
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| CN102676158B (en) * | 2012-05-16 | 2014-07-09 | 陕西师范大学 | Pyrene-contained bis-imidazole type fluorescence probe as well as synthetic method and application thereof |
| CN103242300B (en) * | 2013-04-15 | 2014-06-25 | 天津师范大学 | N-heterocyclic carbene metal complex based on quinoxaline as well as preparation method and application thereof |
| CN104140434B (en) * | 2013-05-09 | 2016-08-03 | 南开大学 | Nitrogen heterocyclic carbene silver complex of double pyrazole alkyl functional and preparation method thereof |
| CN104230965B (en) * | 2014-09-04 | 2016-04-06 | 天津师范大学 | The preparation of ring-type silver complex and the application in identification object thereof |
| CN104910076B (en) * | 2015-05-13 | 2017-03-01 | 天津师范大学 | The preparation of bis-benzimidazole salt and its application in intramolecular coupling reaction |
| CN105646360A (en) * | 2016-01-15 | 2016-06-08 | 天津师范大学 | N-heterocyclic carbene metal complex based on binaphthol link and preparation method and application thereof |
| CN105541876B (en) * | 2016-01-15 | 2017-07-11 | 天津师范大学 | N-heterocyclic carbine metal complex of anthraquinone bridging and preparation method and application |
| CN112169836A (en) * | 2020-09-28 | 2021-01-05 | 广东石油化工学院 | Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same |
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