CN107011208B - It is a kind of chirality organic ligand and its near-infrared rare earth compounding preparation method and application - Google Patents
It is a kind of chirality organic ligand and its near-infrared rare earth compounding preparation method and application Download PDFInfo
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- 239000013110 organic ligand Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract description 35
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 31
- 238000013329 compounding Methods 0.000 title abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 99
- 238000001514 detection method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- AIACXWOETVLBIA-YUMQZZPRSA-N dimethyl (1s,2s)-cyclohexane-1,2-dicarboxylate Chemical compound COC(=O)[C@H]1CCCC[C@@H]1C(=O)OC AIACXWOETVLBIA-YUMQZZPRSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- USJZIUVMYSUNGB-UHFFFAOYSA-N neodymium;hydrate Chemical compound O.[Nd] USJZIUVMYSUNGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims 1
- -1 rare earth ion Chemical class 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000002983 circular dichroism Methods 0.000 description 16
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 159000000000 sodium salts Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 208000020084 Bone disease Diseases 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- AIACXWOETVLBIA-UHFFFAOYSA-N dimethyl cyclohexane-1,2-dicarboxylate Chemical compound COC(=O)C1CCCCC1C(=O)OC AIACXWOETVLBIA-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZTGDSPWWQJFZHL-UHFFFAOYSA-M methanol tetrabutylazanium fluoride Chemical compound [F-].C(CCC)[N+](CCCC)(CCCC)CCCC.CO ZTGDSPWWQJFZHL-UHFFFAOYSA-M 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/04—Preparation of hydrazides
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/21—Polarisation-affecting properties
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
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- 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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Abstract
The invention discloses the preparation method and application of a kind of chiral organic ligand and its rare earth compounding, which has the characteristics that multiple tooth coordination and bridging metal ion, can combine with rare earth ion and form coenocytism；It is chiral single, stable structure four core, four Helical Complex by the rare earth compounding that chiral ligand synthesizes；Such rare earth Helical Complex has Chiral properties and near-infrared luminous characteristic simultaneously；It is formed using the hydrogen bond of NH and fluorine ion on ligand in complex, variation while so as to influence complex chiral signal and near-infrared luminous signal, realizes the various modes selective enumeration method to fluorine ion.
Description
Technical field
The invention belongs to technical field of anion detection, specifically, being related to a kind of chiral organic ligand and its near-infrared
The preparation method and application of rare earth compounding.
Background technique
Fluorine ion is widely present among nature as the smallest anion of electronegativity highest ionic radius, in addition, fluorine from
Son is also one of necessary microelement of human body.The intake of appropriate fluorine ion is beneficial to human body, is added in toothpaste or water suitable
The fluorine ion of amount can prevent saprodontia and osteoporosis.But when the intake of excessive fluorine ion, and fluorine poisoning can be caused, seriously
Person will lead to den tal fluorosis and a series for the treatment of bone diseases.So rule in China's water environment quality standard (GB 3838-2002)
Fixed I class, II class, fluorine (F-) concentration is less than 1.0mg/L, fluorine (F in IV class and V class water in III class water-) concentration be less than 1.5mg/L；
Regulation, fluorine (F in integrated wastewater discharge standard (GB 8978-1996)-) concentration first discharge standard be 10mg/L.Currently,
The method of detection fluorine ion mainly has Fluoride ion selective electrode method, the chromatography of ions, fluorescence analysis, but some detection methods are grasped
It is relatively cumbersome to make step, error is larger, and relatively high to sample requirement, cannot monitor on-line, so developing fluorine ion detection side
Method is particularly important.In recent years, people attempt detection of the various methods for fluorine ion, have especially synthesized various organic spies
Needle compound detects fluorine ion.This kind of detection method based on fluorescence sense response is sensitive, quick, be a kind of important fluorine from
Sub- detection means, but do not have also using the luminous signal variation of chiral near-infrared luminous complex come the research for detecting fluorine ion
Document report.
The near-infrared luminous complex material of rare earth since big with penetration depth, spectral line is narrow, the service life is long, background interference is small and
The features such as harmless to biological tissue, the fields such as fluorescence immunoassay test, optical-fibre communications, anti-fake, laser system and bio-imaging
Through showing the application value that can not be substituted.And the chiral coordination compound for establishing in such material foundation is even more to pass through chiral organic match
Body and coordination with near-infrared luminous rare earth ion, can be realized the knot of the special characteristics of luminescence and Chiral properties
It closes, there is significant application value in fields such as chiral catalysis, separation and identifications, cause the extensive research interest of people.Therefore,
It is a kind of new detection method and means that fluorine ion is detected using the multi-mode signal variation of chiral near-infrared luminous complex,
It is also the important supplement to existing detection method.
Summary of the invention
The purpose of the present invention is to provide the preparation method of a kind of chiral organic ligand and its near-infrared rare earth compounding and
Using.
Itself the specific technical proposal is:
A kind of preparation method of chirality organic ligand, comprising the following steps:
Step 1, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalate: weigh (1R, 2R) or
(1S, 2S) -1,2- cyclohexane cyclohexanedimethanodibasic 1.72g is placed in 50mL round-bottomed flask, and 20mL methanol, concentrated sulfuric acid 1mL, 40 DEG C of stirrings are added
For 24 hours, revolving removes methanol, and organic layer is merged after being extracted with dichloromethane after adding water a little, dry, and revolving removes organic solvent and obtains
To colourless oil liquid (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalate, yield is greater than 80%；
Step 2, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazine: weigh (1R, 2R) or (1S,
2S) -1,2- dimethyl hexahydrophthalate 1.6g is placed in 50mL round-bottomed flask, sequentially adds 25mL methanol, hydrazine hydrate 1.6mL,
Stirred at 40 DEG C for 24 hours, white solid occur, filter, successively washed with methanol, ether, dry white powder (1R, 2R) or
(1S, 2S) -1,2- hexamethylene diformylhydrazine, yield are greater than 70%；
Step 3, synthetic ligands: it weighs (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazine 0.80g and is placed in 50mL circle
Bottom flask, sequentially adds methanol 25mL, and 3- ethyoxyl-Benzaldehyde,2-hydroxy 1.36g methanol solution of 10mL stirs at 40 DEG C
6h is mixed, white solid occurs, filters, is successively washed with methanol, ether, dry that white solid is organic ligand, yield is greater than
70%.
A kind of preparation method of the near-infrared rare earth compounding of chirality organic ligand, comprising the following steps:
Weigh 24.8mg ligand and LiOHH2O 4.2mg is placed in 25mL round-bottomed flask, stirs 5 points after 3mL methanol is added
Clock, then the methanol solution 2mL of six nitric hydrate neodymium 22.0mg is added thereto, quickly stirring is filtered after five minutes, is obtained clear liquid and is set
It slowly volatilizees in room temperature and obtains glassy yellow crystal, yield is greater than 50%.
Application of the near-infrared complex of chirality organic ligand of the present invention in fluorine ion detection process.
Compared with prior art, beneficial effects of the present invention:
The organic ligand that the present invention prepares has the characteristics that multiple tooth coordination and bridging metal ion, can be with rare earth ion knot
Conjunction forms coenocytism；It is chiral single, stable structure four core, four spiral shell by the near-infrared rare earth compounding that chiral ligand synthesizes
Revolve complex；Such rare earth Helical Complex has Chiral properties and near-infrared luminous characteristic simultaneously；It is dilute using such near-infrared
The hydrogen bond of NH and fluorine ion in native complex on ligand are formed, so as to influence complex chiral signal and near-infrared luminous
Change while signal, realizes the various modes selective enumeration method to fluorine ion.
Detailed description of the invention
Fig. 1 is the general formula of the chemical structure of the rare earth neodymium Helical Complex with near-infrared luminous characteristic；
Fig. 2 is the solid-state circular dichroism figure of the corresponding rare earth neodymium Helical Complex of two chiralitys；
Fig. 3 is that a rare earth neodymium Helical Complex responds the circular dichroism of fluorine ion in solution；
Fig. 4 is that the rare earth neodymium Helical Complex with near-infrared luminous characteristic rings the near infrared spectrum of fluorine ion in solution
Answer (excitation wavelength 380nm).
Specific embodiment
Technical solution of the present invention is described in more detail with specific embodiment with reference to the accompanying drawing.
It can be reacted to obtain the chiral near-infrared rare earth compounding with nitric acid rare earth by a kind of chiral organic ligand, specifically
General structure such as Fig. 1.
Opposite hand is respectively provided with by two rare earth Nd complex that the ligand of chiral mapping is prepared using the above method
Property signal, be embodied in circular dichroism (CD) signals that two chiral near-infrared rare earth Nd complex have mirror image mapping,
Such as Fig. 2.
Said one chirality near-infrared rare earth Nd complex responds identification to the optically-active of fluorine ion: there is F in the solution-,
Cl-,Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,F3CSO3 -,HSO4 -When plasma, pass through detection polarimeter detection rotation
The variation of light value, it can be seen that F-It can be substantially change the optical value of complex, such as table 1, table 1 is one with near-infrared luminous
The chiral rare earth neodymium Helical Complex of characteristic is to F in solution-,Cl-,Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,
F3CSO3 -,HSO4 -The optically-active of plasma responds.
Table 1
| Number | Anionic species to be detected | Optical value range (cm-3g-1dm-1) |
| 1 | (only chiral rare earth neodymium Helical Complex, no anion) | - 690~-610 |
| 2 | Chloride ion (Cl-) | - 690~-610 |
| 3 | Bromide ion (Br-) | - 690~-610 |
| 4 | Iodide ion (I-) | - 690~-610 |
| 5 | Nitrate ion (NO3 -) | - 690~-610 |
| 6 | High chloro acid ion (ClO4 -) | - 690~-610 |
| 7 | Nitrine radical ion (N3 -) | - 690~-610 |
| 8 | Hydrogen sulfate ion (HSO4 -) | - 690~-610 |
| 9 | Trifluoromethanesulfonic acid radical ion (F3CSO3 -) | - 690~-610 |
| 10 | Thiocyanate ion (SCN-) | - 690~-610 |
| 11 | Hydroxide ion (OH-) | - 690~-610 |
| 12 | Tetrafluoroborate ion (BF4 -) | - 750~-650 |
| 13 | Fluorine ion (F-) | - 1150~-1050 |
Above-mentioned chirality near-infrared rare earth Nd complex responds identification to circular dichroism (CD) signal of fluorine ion: in solution
In there are F-,Cl-,Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,F3CSO3 -,HSO4 -When plasma, pass through detection CD's
Variation, it can be seen that F-The CD signal of the chirality near-infrared rare earth Nd complex, such as Fig. 3 can be substantially change.
Above-mentioned chirality near-infrared rare earth Nd complex responds identification to the near-infrared of fluorine ion: there is F in the solution-,Cl-,
Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,F3CSO3 -,HSO4 -When plasma, by detecting near-infrared luminous variation,
It can see F-It can be substantially change the near-infrared luminous of the chirality near-infrared rare earth Nd complex, such as Fig. 4.
One, the preparation of chiral ligand
The preparation method of above-mentioned chiral ligand: with (1R, 2R) or (1S, 2S) -1,2- cyclohexane cyclohexanedimethanodibasic for starting material,
It is esterified by the first step plus sulfuric acid catalysis；Second step is added hydrazine hydrate as initial product using first step product and obtains hydrazides；Third
Step, reacts to obtain target chiral organic ligand with salicylic aldehyde derivative as starting material using second step product.
The reaction step of a specific target compound is as follows:
Firstly, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalate: weigh (1R, 2R) or
(1S, 2S) -1,2- cyclohexane cyclohexanedimethanodibasic 1.72g is placed in 50mL round-bottomed flask, and 20mL methanol, concentrated sulfuric acid 1mL, 40 DEG C of stirrings are added
For 24 hours, revolving removes methanol, and organic layer is merged after being extracted with dichloromethane after adding water a little, dry, and revolving removes organic solvent and obtains
To colourless oil liquid (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalate, yield is greater than 80%.Such as (1R, 2R)-
The yield 91.0% of 1,2- dimethyl hexahydrophthalate,(c=0.01g cm-3, solvent: first
Alcohol)；1H NMR(400MHz,CDCl3-d1): δ=3.68 (s, 6H), 2.58-2.65 (m, 2H), 2.05-2.09 (m, 2H),
1.79–1.81(m,2H),1.19–1.43(m,4H).13C NMR(100MHz,CDCl3-d1): δ=175.55,51.82,
44.81,28.94,25.22.ESI,m/z:[M+Na]+223.09。
Then as steps described below, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazine: weigh
(1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalate 1.6g are placed in 50mL round-bottomed flask, sequentially add 25mL methanol,
Hydrazine hydrate 1.6mL is stirred for 24 hours at 40 DEG C, white solid is occurred, filter, successively wash with methanol, ether, the white powder dried
Last (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazine, yield are greater than 70%.Such as two formyl of (1R, 2R) -1,2- hexamethylene
The fusing point of hydrazine: 202.5-203.5 DEG C of(c=0.01g cm-3, solvent: water)；1H NMR
(400MHz,D2O-d2): δ=2.42-2.44 (m, 2H), 1.78-1.87 (m, 4H), 1.28-1.45 (m, 4H)13C NMR
(100MHz,D2O-d2): δ=176.55,45.17,29.39,24.91.ESI, m/z:[M+H]+201.0。
Later, it synthesizes target chiral organic ligand: weighing (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazine
0.80g is placed in 50mL round-bottomed flask, sequentially adds methanol 25mL, 3- ethyoxyl-Benzaldehyde,2-hydroxy 1.36g methanol of 10mL
Solution stirs 6h at 40 DEG C, white solid occurs, filters, is successively washed with methanol, ether, dry that white solid is to have
Machine ligand, yield are greater than 70%.Target chiral ligand (the R)-L such as obtained by (1R, 2R) -1,2- hexamethylene diformylhydrazine
Yield 80.5%.Fusing point: 247.6-248.5 DEG C of(sodium-salt form Na2(R)-L, c=0.01g
cm-3Solvent: methanol)；1H NMR(400MHz,DMSO-d6): δ=11.72 (d, J=16.4Hz, 1.40H), 11.14 (s,
0.6H), 10.83 (d, J=21.6Hz, 1.4H), 9.54 (d, J=21.2Hz, 0.6H), 8.32 (d, J=22.0Hz, 2H),
6.78–7.20(m,6H),4.02–4.08(m,4H),2.50–2.63(m,1.4H),1.79–2.05(m,4H),1.30–1.38
(m,10H).13C NMR(100MHz,DMSO-d6): δ=175.57,171.01,170.69,147.44,147.20,147.10,
146.73,146.50,146.32,141.65,121.11,120.39,119.48,119.08,115.20,114.17,64.22,
44.11,43.88,41.58,29.72,28.49,25.47,25.20,14.90,14.83.ESI,m/z:[M+Na]+
519.2217.Target chiral ligand (the R)-S yield 81.0% obtained by (1S, 2S) -1,2- hexamethylene diformylhydrazine.It is molten
Point: 247.6-248.5 DEG C of(sodium-salt form Na2(S)-L, c=0.01g cm-3Solvent: first
Alcohol).
Two, the preparation of chiral near-infrared rare earth compounding
The wherein preparation step of specific chiral four core of rare earth, four spiral Nd complex: it is chiral to weigh 24.8mg said one
Organic ligand and LiOHH2O 4.2mg is placed in 25mL round-bottomed flask, stirs 5 minutes after 3mL methanol is added, then be added thereto
The methanol solution 2mL of six nitric hydrate neodymium 22.0mg, quickly stirring is filtered after five minutes, obtains clear liquid and be placed in room temperature slowly volatilizing
Glassy yellow crystal is obtained, yield is greater than 50%.Such as the yield of the chirality near-infrared rare earth compounding (1) as made from above-mentioned (R)-L
For 58%, IR (KBr, cm-1):3437(br),3205(m),3051(w),2975(w),2930(m),2859(w),1631(m),
1605(vs),1557(s),1448(s),1384(vs),1301(s),1263(w),1221(vs),1174(m),1097(w),
1070(m),1043(w),938(w),892(m),856(w),741(s),642(w).The chirality as made from above-mentioned (S)-L is close red
The yield of outer rare earth compounding (2) is 53%, IR (KBr, cm-1):3437(br),3212(m),3052(w),2975(w),2930
(m),2859(w),1631(m),1605(vs),1557(s),1448(s),1384(vs),1302(s),1263(w),1220
(vs),1174(m),1097(w),1070(m),1043(w),938(w),891(m),855(w),741(s),642(w).
Rare earth Nd complex Chiral properties obtained above are characterized using solid circular dichroism (CD), can be seen
Out, above-mentioned rare earth Nd complex (1) and complex (2) all have single chiral, and chiral signal is opposite (see Fig. 2)
Three, identification of the near-infrared complex of chiral organic ligand to fluorine ion
1. chiral coordination compound tests the optically-active that fluorine ion responds: configuring the complex methanol solution of 4mM (with organic ligand
Meter), it successively pipettes 2mL complex solution and is placed in the transparent glass bottle of 10mL, amount to 12 bottles, be added thereto respectively
4-butyl ammonium (the F of 2mmol-,Cl-,Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,F3CSO3 -,HSO4 -) methanol solution
Afterwards, after shaking 1 minute, the optical value that different ions are added after complex solution, only optically-active after addition fluorine ion are measured respectively
There are significant changes in value, and numerical value becomes -1150~-1050 (being shown in Table 1) from -690~-610 when being added without ion.Therefore,
It can be by measuring the optical value variation of complex solution as a kind of method for detecting fluorine ion.
2. circular dichroism (CD) test that chiral coordination compound responds fluorine ion: the complex methanol for configuring 0.5mM is molten
Liquid (in terms of organic ligand) pipettes 2mL and sample cell is added, and measurement obtains the circular dichroism figure of complex solution, then, is added
Different amounts of tetrabutyl ammonium fluoride (0.25,0.5,0.75,1.0,2.0 times of amount) measures the circular dichroism of complex solution afterwards
Variation.The intensity of CD is gradually decreased with fluorine ion addition in 254,308 and 400nm, and the peak being located at 235 and 280nm goes out
Now enhance (such as Fig. 3).Therefore it can be by measuring the CD variation of complex solution as a kind of method for detecting fluorine ion.
3. the near-infrared luminous test that chiral coordination compound responds fluorine ion: configure 10mM complex methanol solution (with
Organic ligand meter), 2mL acetonitrile is pipetted in fluorescence cuvette, and the methanol solution of 20 μ L complexs is added, is gradually added dropwise to 0-
2eq tetrabutyl ammonium fluoride methanol solution measures the near-infrared fluorescent spectrum change after the addition of different fluorine ions, In respectively
Emission peak at 1060nm gradually increases (such as Fig. 4) with fluorine ion addition.Therefore, the close red of measurement complex solution can be passed through
It is outer to shine as a kind of method for detecting fluorine ion.
The foregoing is only a preferred embodiment of the present invention, the scope of protection of the present invention is not limited to this, it is any ripe
Know those skilled in the art within the technical scope of the present disclosure, the letter for the technical solution that can be become apparent to
Altered or equivalence replacement are fallen within the protection scope of the present invention.
Claims (3)
1. a kind of preparation method of chirality organic ligand, which comprises the following steps:
Step 1, synthetic intermediate (1S, 2S) -1,2- dimethyl hexahydrophthalate: (1S, 2S) -1,2- hexamethylene diformazan is weighed
Sour 1.72g is placed in 50mL round-bottomed flask, and 20mL methanol is added, and concentrated sulfuric acid 1mL, for 24 hours, revolving removes methanol for 40 DEG C of stirrings, adds water
Merge organic layer after being extracted with dichloromethane after a little, it is dry, revolving remove organic solvent obtain colourless oil liquid (1S,
2S) -1,2- dimethyl hexahydrophthalate, yield are greater than 80%；
Step 2, synthetic intermediate (1S, 2S) -1,2- hexamethylene diformylhydrazine: (1S, 2S) -1,2- cyclohexane cyclohexanedimethanodibasic two is weighed
Methyl esters 1.6g is placed in 50mL round-bottomed flask, sequentially adds 25mL methanol, hydrazine hydrate 1.6mL, stirs for 24 hours at 40 DEG C, white occurs
Solid is filtered, is successively washed with methanol, ether, dry that white powder (1S, 2S) -1,2- hexamethylene diformylhydrazine, yield are big
In 70%；
Step 3, synthetic ligands: weighing (1S, 2S) -1,2- hexamethylene diformylhydrazine 0.80g and be placed in 50mL round-bottomed flask, successively plus
Enter methanol 25mL, 3- ethyoxyl-Benzaldehyde,2-hydroxy 1.36g methanol solution of 10mL stirs 6h at 40 DEG C, white occurs
Solid is filtered, is successively washed with methanol, ether, and dry that white solid is organic ligand, yield is greater than 70%；It is chiral organic
The structural formula of ligand is as follows:
2. a kind of preparation method of the complex for the chiral organic ligand that claim 1 the method obtains, which is characterized in that packet
Include following steps:
Weigh 24.8mg ligand and LiOHH2O 4.2mg is placed in 25mL round-bottomed flask, stirs 5 minutes after 3mL methanol is added, then
The methanol solution 2mL of six nitric hydrate neodymium 22.0mg is added thereto, quickly stirring is filtered after five minutes, is obtained clear liquid and is placed in room
Warm slowly volatilization obtains glassy yellow crystal, and yield is greater than 50%；The structural formula of the complex of chiral organic ligand is as follows:
3. application of the complex of chirality organic ligand in fluorine ion detection process described in claim 2.
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Inventor after: Tang Xiaoliang Inventor after: Chen Wanmin Inventor after: Liu Weisheng Inventor after: Zhu Hao Inventor before: Tang Xiaoliang Inventor before: Chen Wanmin Inventor before: Liu Weisheng |