CN102675373B - Methanol indicator and preparation method thereof - Google Patents
Methanol indicator and preparation method thereof Download PDFInfo
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- CN102675373B CN102675373B CN201210099052.XA CN201210099052A CN102675373B CN 102675373 B CN102675373 B CN 102675373B CN 201210099052 A CN201210099052 A CN 201210099052A CN 102675373 B CN102675373 B CN 102675373B
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- methanol
- dceb
- methyl alcohol
- indicator
- nbu
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Abstract
The invention relates to a methanol indicator and a preparation method thereof. The methanol indicator disclosed by the invention is Fe2Co2 four-core compound bridged by cyano group and has a chemical formula of [Co2Fe2(CN)6(Tp)2(4,4'-DCEB)4](ClO4)2, wherein Tp is triparazole borate; and DCEB is 2,2-bipyridyl-4,4-ethylene terephthalate. The methanol indicator is displayed to be red in a general state and is immediately turned into green only when the methanol indicator is in contact with a methanol solvent. The structure of a compound which is displayed to be green after the methanol indicator is in contact with the methanol solvent is determined by X-ray single crystal diffraction and is verified to a square planar Fe2Co2 four-core compound bridged by the cyano group. The square planar Fe2Co2 four-core compound has a molecular formula of [Co2Fe2(CN)6(Tp)2(4,4'-DCEB)4](ClO4)2.2MeOH, wherein MeOH is methanol. The methanol indicator disclosed by the invention shows highly-selective response to methanol molecules and has no response to other various alcohol solvents and other various non-alcohol solvents. The methanol indicator disclosed by the invention has the advantages of simpleness in synthesis, easy operation, quickness in response, distinct color change and indication, capability of recycling and the like.
Description
Technical field
The present invention relates to a kind of methyl alcohol indicator molecules and preparation method thereof.
Background technology
Personation industrial spirit exchange white wine with high concentration methanol, causes poisoning, makes thousands of people poisoning, and hundreds of people is dead, and this is the methyl alcohol acute poisoning accident that people know and fear.What is more, and some enterprises, in order to seek larger profit, palm off alcohol (ethanol) with methyl alcohol and mix in gasoline.Reason is that the price of methyl alcohol is about half of alcohol, and Here it is palms off the root that industrial spirit overflows.And the outward appearance of methyl alcohol, smell, mouthfeel, density, combustion position and alcohol are very approximate, be difficult to distinguish them with simple and easy methods such as sense organs.And for how simple, effective, convenient and rapid detection methyl alcohol, report both domestic and external is very few.Several methyl alcohol detection methods of commonly using at present or expensive, or waste time and energy, all can not meet well cheap, demand easily and fast in daily life.
Summary of the invention
The object of this invention is to provide a kind of new methyl alcohol indicator and preparation method thereof.The present invention can overcome the defect of prior art effectively, compound of the present invention be one by the planar Fe of cyanide-bridged chromium
2co
2four core coordination compoundes.
The chemical formula of methyl alcohol indicator title complex of the present invention is [Co
2fe
2(CN)
6(Tp)
2(4,4 '-DCEB)
4] (ClO
4)
2, wherein Tp is tripyrozoleyelborate, DCEB is 2,2 '-dipyridyl-4,4 '-dioctyl phthalate ethyl ester.
Methyl alcohol indicator title complex of the present invention, is characterized in that: its methyl alcohol bonding state molecular formula is: [Co
2fe
2(CN)
6(Tp)
2(4,4 '-DCEB)
4] (ClO
4)
2.2MeOH, as shown in Figure 1, its crystalline structure is crystalline structure: be oblique system, spacer is
p2
1/ n, unit cell parameters is:
a=15.6722 (11),
b=17.9250 (12),
c=18.8010 (13),
α=90.00 degree,
β=107.0780 (10) degree,
γ=90.00 degree; this compound forms four nuclear compounds of planar shape by two Fe and two Co through cyanide-bridged chromium, main bond distance's () is: Co (1)-N (2) 1.8758 (19), Co (1)-N (1) 1.8839 (19), Co (1)-N (13) 1.9254 (19), Co (1)-N (12) 1.9310 (19), Co (1)-N (11) 1.9339 (18), Co (1)-N (10) 1.9356 (19), Fe (1)-C (1) 1.851 (2), Fe (1)-C (2) 1.852 (2), Fe (1)-C (3) 1.907 (3), Fe (1)-N (8) 1.9942 (19), Fe (1)-N (6) 2.001 (2), Fe (1)-N (4) 2.009 (2).
The preparation method of methyl alcohol indicator of the present invention comprises the steps:
1) by general preparation method, prepare respectively (NBu
4) [(Tp) Fe (CN)
3] and DCEB;
2) with anhydrous methanol by Co (ClO
4)
2.6H
2o and DCEB mix, and stir 2 hours to dissolving completely, add (NBu
4) [(Tp) Fe (CN)
3], continue to stir 2 hours; (NBu wherein
4) [(Tp) Fe (CN)
3], Co (ClO
4)
2.6H
2the mol ratio of O and DCEB is 1:1:2.
3), filter, vacuum-drying obtains red target product: [Co
2fe
2(CN)
6(Tp)
2(4,4 '-DCEB)
4] (ClO
4)
2.
If filtrate at room temperature standing a couple of days have green crystal to separate out, be the methyl alcohol binding substances of target product.
In State Standard of the People's Republic of China GB/T 394.2-1994 alcohol common reagent methods, show 3 kinds of methyl alcohol methods of inspection: the first method vapor-phase chromatography, the second method chromotropic acid colorimetry, third method magenta-sulfurous acid colorimetry.Vapor-phase chromatography is easy fast, but instrument price is more expensive, cannot afford in general laboratory.Colorimetry will be prepared a series of reagent, and operation steps is more, time-consuming, and its application is restricted.The present invention overcomes the defect of prior art effectively, can realize rapid detection methyl alcohol, and processing ease, synthetic simple, thereby has the possibility of widespread use.And this compound can recycle, there is the feature of high-efficiency environment friendly, therefore methyl alcohol indicator of the present invention can be widely used in practice test.
Accompanying drawing explanation
Fig. 1. the methyl alcohol binding substances [Co of methyl alcohol indicator of the present invention
2fe
2(CN)
6(Tp)
2(4,4 '-DCEB)
4] (ClO
4)
2.2MeOH crystalline structure figure (for the purpose of clear demonstration, having ignored hydrogen atom, negatively charged ion and solvent molecule).
Fig. 2, the synthetic methyl alcohol indicator product photo obtaining of the present invention.
In Fig. 3, the synthetic methyl alcohol indicator obtaining of the present invention, drip the methyl alcohol adducts photo after methyl alcohol.
Methyl alcohol indicator photo after the methyl alcohol volatilization dripping in Fig. 4, the synthetic methyl alcohol indicator obtaining of the present invention.
Embodiment
Embodiment 1 (NBu
4) [(Tp) Fe (CN)
3] synthetic:
Take FeCl
2.2H
2o 1.2 g and KTp 4 g, add methyl alcohol 30 ml, filters after stirring 2 h, adds methyl alcohol 30 ml after abandoning filtrate again, and the aqueous solution of 1.36 g NaCN is added wherein, and 60 ℃ of stirrings are spent the night.Except desolventizing, solid is dissolved in hot water (70～80 ℃), and filtered while hot adds NBu after filtrate is cooling
4br (Tetrabutyl amonium bromide) 7 g, gradation adds 30% H
2o
220 ml, stir after 10 h, produce orange red solid, collect solid, after ether washing, dry, and mix or spread ether recrystallization to obtain orange red crystal in methanol solution.
Embodiment 2 DCEB's is synthetic
Take 4 g 2,2 '-dipyridyl-4,4 '-dioctyl phthalate, in 30 ml ethanol, then splashes into the 4 ml vitriol oils, stirs reflux 120 h.Remove ethanol, in residuum, add 5 ml water, in sodium carbonate, with rear generation white solid, collect solid, the dry white powder that to obtain of washing final vacuum.Productive rate: 68%.
Synthetic and the sign of embodiment 3 methyl alcohol indicator title complexs
(1) synthetic: in beaker, to add Co (ClO
4)
2.6H
2o 46 mg and above-mentioned synthetic DCEB 75 mg, then add 20 ml anhydrous methanols, be stirred to completely and dissolve, add (NBu
4) [(Tp) Fe (CN)
3] 70 mg, continue to stir after 2 h, to filter, the red powder that rotary evaporation is removed after volatile solvent is target compound.In addition, if filtrate can be obtained to green crystal after standing one week, productive rate 60% (171 mg), is the methyl alcohol adducts of target product.
(2) crystal structure determination of methyl alcohol indicator title complex methyl alcohol adducts
Select a size to be about the green crystal of 0.08 * 0.12 * 0.35 mm, on Bruker APEX-II CCD x-ray diffractometer, using the Mo K alpha-ray (λ=0.71703) through graphite monochromatization is light source, measuring temperature is 100 (2) K, from 37720 point diffractions, through least-squares refinement, obtain unit cell parameters, from difference Fourier electron density map, utilize SHELXL-97 direct method to solve crystalline structure.All H atoms are synthesized by difference Fourier and determine through desirable position calculation.The final consistence factor is
r 1=0.0336,
wR 2=0.0955(I > 2 σ (I));
r 1=0.0435,
wR 2the all data of=0.1042().In final difference Fourier electron density map, peak-peak is 1.05 e
-3.Detailed axonometry data are in Table 1.
Table 1 title complex [Co
2fe
2(CN)
6(Tp)
2(4,4 '-DCEB)
4] (ClO
4)
2.2MeOH crystallographic data
[0019](3) character of methyl alcohol indicator title complex and application
On dried target title complex sample, splash into respectively various organic solvent (methyl alcohol, ethanol, Virahol, isopropylcarbinol, acetonitrile, acetone, methylene dichloride, trichloromethane, Nitromethane 99Min. etc.), except splashing into the red powder of methyl alcohol, become at once green, remaining solvent is not all any change within the test duration; And run into methyl alcohol and turn green powder and after solvent evaporates, revert to again redness, this process can repeat (seeing Fig. 2,3,4).To possible interference solution (as: diluted acid, diluted alkaline, ammoniacal liquor, metal ion etc.), test also shows that this compound has good immunity from interference in addition.Result shows that this compound only has special single-minded indication ability to methanol molecules.
Claims (5)
1. a methyl alcohol indicator, is characterized in that: it is the coordination compound of following chemical formula: [Co
2fe
2(CN)
6(Tp)
2(DCEB)
4] (ClO
4)
2, wherein Tp is three pyrazoles borates, DCEB is 2,2 '-dipyridyl-4,4 '-dioctyl phthalate ethyl ester.
2. the methyl alcohol binding substances of methyl alcohol indicator claimed in claim 1, is characterized in that: chemical formula is: [Co
2fe
2(CN)
6(Tp)
2(DCEB)
4] (ClO
4)
2.2MeOH, crystalline structure is: be oblique system, spacer is
p2
1/ n, unit cell parameters is:
a=15.6722 (11),
b=17.9250 (12),
c=18.8010 (13),
α=90.00 degree,
β=107.0780 (10) degree,
γ=90.00 degree, main bond distance is: Co (1)-N (2) 1.8758 (19), Co (1)-N (1) 1.8839 (19), Co (1)-N (13) 1.9254 (19), Co (1)-N (12) 1.9310 (19), Co (1)-N (11) 1.9339 (18), Co (1)-N (10) 1.9356 (19), Fe (1)-C (1) 1.851 (2), Fe (1)-C (2) 1.852 (2), Fe (1)-C (3) 1.907 (3), Fe (1)-N (8) 1.9942 (19), Fe (1)-N (6) 2.001 (2), Fe (1)-N (4) 2.009 (2).
3. the preparation method of methyl alcohol indicator claimed in claim 1, is characterized in that it comprises the steps:
1) prepare respectively (NBu
4) [(Tp) Fe (CN)
3] and DCEB;
2) with anhydrous methanol by Co (ClO
4)
2.6H
2o and DCEB dissolve completely, then add (NBu
4) [(Tp) Fe (CN)
3], described (NBu
4) [(Tp) Fe (CN)
3], Co (ClO
4)
2.6H
2the mol ratio of O and DCEB is 1:1:2, continues to stir 2 hours;
3) filter, remove volatile matter, after vacuum-drying, obtain red target product.
4. according to the preparation method of methyl alcohol indicator claimed in claim 3, it is characterized in that (NBu
4) [(Tp) Fe (CN)
3] synthetic: take FeCl
2.2H
2o 1.2 g and KTp 4 g, add methyl alcohol 30 ml, filters after stirring 2 h, adds methyl alcohol 30 ml after abandoning filtrate again, the aqueous solution of 1.36 g NaCN is added wherein, and 60 ℃ of stirrings are spent the night, except desolventizing, solid is dissolved in hot water, and filtered while hot adds NBu after filtrate is cooling
4br 7 g, gradation adds 30wt% H
2o
220 ml, stir after 10 h, produce orange red solid, collect solid, after ether washing, dry, and mix or spread ether recrystallization to obtain orange red crystal in methanol solution.
5. according to the preparation method of methyl alcohol indicator claimed in claim 3, it is characterized in that, DCEB's is synthetic: take 4 g 2,2 '-dipyridyl-4,4 '-dioctyl phthalate, in 30 ml ethanol, then splashes into the 4 ml vitriol oils, stirs, reflux 120 h, remove ethanol, in residuum, add 5 ml water, in sodium carbonate and rear generation white solid, collect solid, washing final vacuum is dried to obtain white powder DCEB.
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|---|---|---|---|
| CN201210099052.XA CN102675373B (en) | 2012-04-06 | 2012-04-06 | Methanol indicator and preparation method thereof |
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| CN102675373B true CN102675373B (en) | 2014-08-27 |
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Families Citing this family (2)
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| CN114621262B (en) * | 2020-12-14 | 2023-11-28 | 中国科学院大连化学物理研究所 | Preparation and application of metal nanocluster material for rapidly detecting methanol |
| CN113198637B (en) * | 2021-04-07 | 2022-03-15 | 太原理工大学 | Spraying device and method for detecting multi-carbon alcohol in methanol gasoline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5627164A (en) * | 1995-06-13 | 1997-05-06 | Exxon Research And Engineering Company | Pyrazolyl borates complexes-(LAW294) |
| WO2003070737A1 (en) * | 2002-02-21 | 2003-08-28 | Polimeri Europa S.P.A. | Nickel tris-pyrazolyl borate complexes and their use |
| CN1624070A (en) * | 2004-10-22 | 2005-06-08 | 友达光电股份有限公司 | Organic metal complex and organic electroluminescent apparatus containing said organic metal complex |
-
2012
- 2012-04-06 CN CN201210099052.XA patent/CN102675373B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5627164A (en) * | 1995-06-13 | 1997-05-06 | Exxon Research And Engineering Company | Pyrazolyl borates complexes-(LAW294) |
| WO2003070737A1 (en) * | 2002-02-21 | 2003-08-28 | Polimeri Europa S.P.A. | Nickel tris-pyrazolyl borate complexes and their use |
| CN1624070A (en) * | 2004-10-22 | 2005-06-08 | 友达光电股份有限公司 | Organic metal complex and organic electroluminescent apparatus containing said organic metal complex |
Non-Patent Citations (8)
| Title |
|---|
| Controlled Intramolecular Electron Transfers in Cyanide-Bridged Molecular Squares by Chemical Modifications and External Stimuli;Nihei Masayuki等,;《Journal of the American Chemical Society》;20110222;第133卷(第10期);第3592-3600页 * |
| Controlling Thermally Induced Electron Transfer in Cyano-Bridged Molecular Squares: From Solid State to Solution;Siretanu Diana等,;《Chemistry-A European Journal》;20110909;第17卷(第42期);第11704-11708页 * |
| Nihei Masayuki等,.Controlled Intramolecular Electron Transfers in Cyanide-Bridged Molecular Squares by Chemical Modifications and External Stimuli.《Journal of the American Chemical Society》.2011,第133卷(第10期),第3592-3600页. |
| Pardo Emilio等,.Synthesis, Crystal Structures, and Magnetic Properties of a New Family of Heterometallic Cyanide-Bridged FeIII2MII2 (M = Mn, Ni, and Co) Square Complexes.《Inorganic Chemistry》.2011,第50卷(第13期),第6250-6262页. |
| Reversible Thermally and Photoinduced Electron Transfer in a Cyano-Bridged {Fe2Co2} Square Complex;Yuanzhu Zhang等,;《Angewandte Chemie》;20100421;第122卷;第3840-3844页 * |
| Siretanu Diana等,.Controlling Thermally Induced Electron Transfer in Cyano-Bridged Molecular Squares: From Solid State to Solution.《Chemistry-A European Journal》.2011,第17卷(第42期),第11704-11708页. |
| Synthesis, Crystal Structures, and Magnetic Properties of a New Family of Heterometallic Cyanide-Bridged FeIII2MII2 (M = Mn, Ni, and Co) Square Complexes;Pardo Emilio等,;《Inorganic Chemistry》;20110601;第50卷(第13期);第6250-6262页 * |
| Yuanzhu Zhang等,.Reversible Thermally and Photoinduced Electron Transfer in a Cyano-Bridged {Fe2Co2} Square Complex.《Angewandte Chemie》.2010,第122卷第3840-3844页. |
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