CN107011208A - A kind of preparation method and application of chiral organic ligand and its near-infrared rare earth compounding - Google Patents
A kind of preparation method and application of chiral organic ligand and its near-infrared rare earth compounding 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
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 238000003756 stirring Methods 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 class COC(=O)[C@H]1CCCC[C@@H]1C(=O)OC AIACXWOETVLBIA-YUMQZZPRSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- 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
- -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
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 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
- 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
- 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
- 150000001450 anions Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 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
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 159000000000 sodium salts Chemical group 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
- 241000370738 Chlorion Species 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
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 238000011161 development Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 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
- 238000005259 measurement Methods 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
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
-
- G—PHYSICS
- 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
-
- G—PHYSICS
- 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
- G01N21/25—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
-
- 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
Abstract
The invention discloses a kind of preparation method and application of chiral organic ligand and its rare earth compounding, the organic ligand has multiple tooth coordination and bridging metal ion feature, can combine to form coenocytism with rare earth ion；The rare earth compounding synthesized by chiral ligand is chiral single, the constitutionally stable Helical Complex of four core four；Such rare earth Helical Complex has Chiral properties and near-infrared luminous characteristic simultaneously；Formed using the NH and the hydrogen bond of fluorine ion on part in complex, so as to influence to change while complex chiral signal and near-infrared luminous signal, realize the various modes selective enumeration method to fluorine ion.
Description
Technical field
The invention belongs to technical field of anion detection, specifically, it is related to a kind of chiral organic ligand and its near-infrared
The preparation method and application of rare earth compounding.
Background technology
Fluorine ion is widely present among nature as the minimum anion of electronegativity highest ionic radius, in addition, fluorine from
Son is also one of necessary trace element 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 carious tooth and osteoporosis.But, when excessive fluorine ion is taken in, fluorine poisoning can be caused again, seriously
Person can cause den tal fluorosis and a series for the treatment of bone diseases.So, advised in China's water environment quality standard (GB 3838-2002)
Fluorine (F-) concentration is less than fluorine (F in 1.0mg/L, IV class and V class water in fixed I class, II class, III class water-) concentration be less than 1.5mg/L；
Provided in integrated wastewater discharge standard (GB 8978-1996), fluorine (F-) concentration first discharge standard be 10mg/L.At present,
The method of detection fluorine ion mainly has Fluoride ion selective electrode method, the chromatography of ions, XRF, but some detection methods are grasped
Make step relatively cumbersome, error is larger, and it is higher to sample requirement, it is impossible to monitor on-line, so development fluorine ion detection side
Method is particularly important.In recent years, people, which attempt various methods, is used for the detection of fluorine ion, has particularly synthesized various organic spies
Pin compound detects fluorine ion.This kind of detection method responded based on fluorescence sense is sensitive, quick, be a kind of important fluorine from
Sub- detection means, but the research changed using the luminous signal of chiral near-infrared luminous complex to detect fluorine ion is not had also
Document report.
The near-infrared luminous complex material of rare earth due to penetration depth is big, spectral line is narrow, long lifespan, ambient interferences it is small and
The features such as harmless to biological tissue, in fields such as fluorescence immunoassay test, optical-fibre communications, false proof, laser system and bio-imagings
The application value that can not be substituted through showing.And foundation is even more to match somebody with somebody by the way that chirality is organic in the chiral coordination compound of such material foundation
Body and the coordination with near-infrared luminous rare earth ion, can realize the knot of the special characteristics of luminescence and Chiral properties
Close, there is significant application value in fields such as chiral catalysis, separation and identifications, the extensive research interest of people is caused.Therefore,
Change to detect that fluorine ion is a kind of new detection method and means using the multi-mode signal of chiral near-infrared luminous complex,
It is also the important supplement to existing detection method.
The content of the invention
It is an object of the invention to provide a kind of preparation method of chiral organic ligand and its near-infrared rare earth compounding and
Using.
Its concrete technical scheme is：
A kind of preparation method of chiral organic ligand, comprises the following steps：
Step 1, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalates：Weigh (1R, 2R) or
(1S, 2S) -1,2- cyclohexane cyclohexanedimethanodibasics 1.72g is placed in 50mL round-bottomed flasks, adds 20mL methanol, concentrated sulfuric acid 1mL, 40oC stirring
24h, revolving removes methanol, merges organic layer after being extracted after adding water a little with dichloromethane, dries, and revolving removes organic solvent and obtained
To colourless oil liquid (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalates, yield is more than 80%；
Step 2, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazines：Weigh (1R, 2R) or (1S,
2S) -1,2- dimethyl hexahydrophthalates 1.6g is placed in 50mL round-bottomed flasks, sequentially adds 25mL methanol, hydrazine hydrate 1.6mL,
Stir 24h under 40oC, white solid occur, suction filtration is washed with methanol, ether successively, dry white powder (1R, 2R) or
(1S, 2S) -1,2- hexamethylene diformylhydrazines, yield is more than 70%；
Step 3, synthetic ligands：Weigh (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazines 0.80g and be placed in 50mL circles
Bottom flask, sequentially adds methanol 25mL, 10mL 3- ethyoxyls-Benzaldehyde,2-hydroxy 1.36g methanol solution, is stirred under 40oC
6h is mixed, white solid occurs, suction filtration is washed with methanol, ether successively, dry that white solid is organic ligand, yield is more than
70%.
A kind of preparation method of the near-infrared rare earth compounding of chiral organic ligand, comprises the following steps：
Weigh 24.8mg parts and LiOHH2O 4.2mg are placed in 25mL round-bottomed flasks, add and 5 points are stirred after 3mL methanol
Clock, then six nitric hydrate neodymium 22.0mg methanol solution 2mL is added thereto, quick stirring is filtered after 5 minutes, obtains clear liquid and put
Slowly volatilized in room temperature and obtain glassy yellow crystal, yield is more than 50%.
Application of the near-infrared complex of chiral 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 is prepared has multiple tooth coordination and bridging metal ion feature, can be with rare earth ion knot
Conjunction forms coenocytism；The near-infrared rare earth compounding synthesized by chiral ligand is chiral single, the constitutionally stable spiral shell of four core four
Screw compound；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 part are formed, so as to influence complex chiral signal and near-infrared luminous
Change while signal, realize the various modes selective enumeration method to fluorine ion.
Brief description of the drawings
Fig. 1 is the chemical structure of general formula 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 is responded to the circular dichroism of fluorine ion in solution；
Fig. 4 is that the rare earth neodymium Helical Complex with near-infrared luminous characteristic rings to the near infrared spectrum of fluorine ion in solution
Answer (excitation wavelength is 380nm).
Embodiment
Technical scheme is described in more detail with specific embodiment below in conjunction with the accompanying drawings.
The chiral near-infrared rare earth compounding can be obtained with nitric acid rare earth reaction by the chiral organic ligand of a class, specifically
General structure such as Fig. 1.
The two rare earth Nd complex prepared using the above method by the part of chiral mapping have opposite hand respectively
Property signal, being embodied in two chiral near-infrared rare earth Nd complex has circular dichroism (CD) signal of mirror image mapping,
Such as Fig. 2.
Optically-active of the said one chirality near-infrared rare earth Nd complex to fluorine ion, which is responded, to be recognized：There is F in the solution-,
Cl-,Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,F3CSO3 -,HSO4 -During plasma, by detecting polarimeter detection rotation
The change of light value, it can be seen that F-The optical value of complex, such as table 1 can substantially be changed, 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 response of plasma.
Table 1
| Numbering | Anionic species to be detected | Optical value scope (cm-3g-1dm-1) |
| 1 | (only chiral rare earth neodymium Helical Complex, no anion) | - 690~-610 |
| 2 | Chlorion (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 chiral near-infrared rare earth Nd complex is responded to circular dichroism (CD) signal of fluorine ion and recognized：In solution
In there is F-,Cl-,Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,F3CSO3 -,HSO4 -During plasma, by detecting CD's
Change, it can be seen that F-The CD signals of the chiral near-infrared rare earth Nd complex, such as Fig. 3 can substantially be changed.
Above-mentioned chiral near-infrared rare earth Nd complex is responded to the near-infrared of fluorine ion and recognized：There is F in the solution-,Cl-,
Br-,I-,NO3 -,OH-,BF4 -,ClO4 -,N3 -,SCN-,F3CSO3 -,HSO4 -During plasma, the near-infrared luminous change by detecting,
It can be seen that F-The near-infrared luminous of the chiral near-infrared rare earth Nd complex can substantially be changed, such as Fig. 4.
First, the preparation of chiral ligand
The preparation method of above-mentioned chiral ligand：With (1R, 2R) or (1S, 2S) -1,2- cyclohexane cyclohexanedimethanodibasics for initiation material,
It is esterified by the first step plus sulfuric acid catalysis；Second step, hydrazine hydrate is added by initial product of first step product and obtains hydrazides；3rd
Step, target chiral organic ligand is obtained by initiation material of second step product with salicylic aldehyde derivative reaction.
The reactions steps of a specific target compound are as follows：
First, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalates：Weigh (1R, 2R) or
(1S, 2S) -1,2- cyclohexane cyclohexanedimethanodibasics 1.72g is placed in 50mL round-bottomed flasks, adds 20mL methanol, concentrated sulfuric acid 1mL, 40 DEG C of stirrings
24h, revolving removes methanol, merges organic layer after being extracted after adding water a little with dichloromethane, dries, and revolving removes organic solvent and obtained
To colourless oil liquid (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalates, yield is more than 80%.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 diformylhydrazines：Weigh
(1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalates 1.6g are placed in 50mL round-bottomed flasks, sequentially add 25mL methanol,
Hydrazine hydrate 1.6mL, 40o24h is stirred under C, white solid occurs, suction filtration is washed with methanol, ether successively, the white powder dried
Last (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazines, yield are more than 70%.Such as the formyl of (1R, 2R) -1,2- hexamethylenes two
The yield 61.2%. fusing points of hydrazine：202.5–203.5oC.(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。
Afterwards, target chiral organic ligand is synthesized：Weigh (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazines
0.80g is placed in 50mL round-bottomed flasks, sequentially adds methanol 25mL, 10mL 3- ethyoxyls-Benzaldehyde,2-hydroxy 1.36g methanol
Solution, 6h is stirred under 40oC, white solid occurs, and suction filtration is washed with methanol, ether successively, dry that white solid is to have
Machine part, yield is more than 70%.Target chiral part (the R)-L such as obtained by (1R, 2R) -1,2- hexamethylene diformylhydrazines
Yield 80.5%.Fusing point：247.6–248.5℃.(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 part (the R)-S yield 81.0% obtained by (1S, 2S) -1,2- hexamethylene diformylhydrazines.It is molten
Point：247.6–248.5℃.(sodium-salt form Na2(S)-L, c=0.01g cm-3Solvent：First
Alcohol).
2nd, the preparation of chiral near-infrared rare earth compounding
The preparation process of the wherein specific chiral spiral Nd complex of four core of rare earth four：Weigh 24.8mg said ones chiral
Organic ligand and LiOHH2O 4.2mg are placed in 25mL round-bottomed flasks, add after 3mL methanol and stir 5 minutes, then add thereto
Six nitric hydrate neodymium 22.0mg methanol solution 2mL, quick stirring is filtered after 5 minutes, obtains clear liquid and be placed in room temperature slowly volatilizing
Glassy yellow crystal is obtained, yield is more than 50%.Such as the yield of the chiral 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).It is chiral near red as made from above-mentioned (S)-L
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
Go out, above-mentioned rare earth Nd complex (1) and complex (2) all have single chiral, and chiral signal is opposite (see Fig. 2)
3rd, identification of the near-infrared complex of chiral organic ligand to fluorine ion
1. the optically-active test that chiral coordination compound is responded to fluorine ion：4mM complex methanol solution is configured (with organic ligand
Meter), 2mL complex solutions are pipetted successively and are placed in 10mL clear glass bottle, 12 bottles altogether, are added thereto respectively
2mmol 4-butyl ammonium (F-,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 is measured respectively, optically-active after fluorine ion is only added
There are significant changes in value, and its numerical value is changed into -1150~-1050 (being shown in Table 1) from -690~-610 when being added without ion.Therefore,
A kind of method for detecting fluorine ion can be used as by measuring the optically-active value changes of complex solution.
2. circular dichroism (CD) test that chiral coordination compound is responded to fluorine ion：The complex methanol for configuring 0.5mM is molten
Liquid (in terms of organic ligand), pipettes 2mL and adds sample cell, measurement obtains the circular dichroism figure of complex solution, then, adds
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
Change.CD intensity is added with fluorine ion in 254,308 and 400nm and gradually reduced, and the peak at 235 and 280nm goes out
Now strengthen (such as Fig. 3).Therefore CD changes that can be by measuring complex solution are used as a kind of method for detecting fluorine ion.
3. the near-infrared luminous test that chiral coordination compound is responded to fluorine ion：Configure 10mM complex methanol solution (with
Organic ligand meter), 2mL acetonitriles are pipetted in fluorescence cuvette, are added the methanol solution of 20 μ L complexs, are gradually added dropwise to 0-
2eq tetrabutyl ammonium fluorides methanol solution measures the near-infrared fluorescent spectrum change after the addition of different fluorine ions respectively,
Emission peak at 1060nm is added with fluorine ion gradually strengthens (such as Fig. 4).It therefore, it can by measuring the near red of complex solution
Outer light is used as a kind of method for detecting fluorine ion.
The foregoing is only a preferred embodiment of the present invention, protection scope of the present invention not limited to this, any ripe
Those skilled in the art are known in the technical scope of present disclosure, the letter for the technical scheme that can be become apparent to
Altered or equivalence replacement are each fallen within protection scope of the present invention.
Claims (3)
1. a kind of preparation method of chiral organic ligand, it is characterised in that comprise the following steps：
Step 1, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalates：Weigh (1R, 2R) or (1S,
2S) -1,2- cyclohexane cyclohexanedimethanodibasics 1.72g is placed in 50mL round-bottomed flasks, adds 20mL methanol, the concentrated sulfuric acid 1mL, 40 DEG C of stirring 24h,
Revolving removes methanol, merges organic layer after being extracted after adding water a little with dichloromethane, dries, and revolving removes organic solvent and obtains nothing
Color oily liquids (1R, 2R) or (1S, 2S) -1,2- dimethyl hexahydrophthalates, yield are more than 80%；
Step 2, synthetic intermediate (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazines：Weigh (1R, 2R) or (1S, 2S)-
1,2- dimethyl hexahydrophthalate 1.6g is placed in 50mL round-bottomed flasks, sequentially adds 25mL methanol, hydrazine hydrate 1.6mL, 40 DEG C
, there is white solid in lower stirring 24h, and suction filtration is washed with methanol, ether successively, dry white powder (1R, 2R) or (1S,
2S) -1,2- hexamethylene diformylhydrazines, yield is more than 70%；
Step 3, synthetic ligands：Weigh (1R, 2R) or (1S, 2S) -1,2- hexamethylene diformylhydrazines 0.80g and be placed in 50mL round bottoms burning
Bottle, sequentially adds methanol 25mL, 10mL 3- ethyoxyls-Benzaldehyde,2-hydroxy 1.36g methanol solution, is stirred at 40 DEG C
, there is white solid in 6h, and suction filtration is washed with methanol, ether successively, and dry that white solid is organic ligand, yield is more than
70%.
2. a kind of preparation method of the complex of chiral organic ligand, it is characterised in that comprise the following steps：
Weigh 24.8mg parts and LiOHH2O 4.2mg are placed in 25mL round-bottomed flasks, add after 3mL methanol and stir 5 minutes, then
Six nitric hydrate neodymium 22.0mg methanol solution 2mL is added thereto, and quick stirring is filtered after 5 minutes, is obtained clear liquid and is placed in room
Warm slow volatilization obtains glassy yellow crystal, and yield is more than 50%.
3. application of the complex of chiral organic ligand in fluorine ion detection process described in claim 2.
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| CN105911041A (en) * | 2016-06-01 | 2016-08-31 | 章健 | Time-resolved fluorescence detection method |
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| CN105911041A (en) * | 2016-06-01 | 2016-08-31 | 章健 | Time-resolved fluorescence detection method |
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| AMIT KUMAR MONDAL ET AL.: "Lanthanide-Directed Fabrication of Four Tetranuclear Quadruple Stranded Helicates Showing Magnetic Refrigeration and Slow Magnetic Relaxation", 《INORGANIC CHEMISTRY》 * |
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