CN104628614A - Metal-dithiene complex and use thereof - Google Patents
Metal-dithiene complex and use thereof Download PDFInfo
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- CN104628614A CN104628614A CN201510026716.3A CN201510026716A CN104628614A CN 104628614 A CN104628614 A CN 104628614A CN 201510026716 A CN201510026716 A CN 201510026716A CN 104628614 A CN104628614 A CN 104628614A
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Abstract
The invention relates to a metal-dithiene complex and a use thereof. The metal-dithiene complex is a compound represented by the formula I as shown in the description, wherein R is a linear-chain or branched-chain alkenyl or phenyl-substituted linear-chain or branched-chain alkenyl and M is metal elements of Group VIII and Group IB contained in the periodic table. The metal-dithiene complex provided by the invention has good solubility in an organic solvent and can be copolymerized with monomers which constitute a goggle having infrared absorbing property and the obtained copolymer is good in infrared absorption property and can be used for preparing the goggle having infrared absorption property.
Description
Technical field
The present invention relates to a kind of dithiolene metal complexes and uses thereof, specifically, relate to a kind of side chain containing unsaturated substituent dithiolene metal complexes and uses thereof.
Background technology
In recent years, along with the continuous progress of laser technology, it is applied in industries such as communication, automobile making, household electrical appliance, medical treatment.Although laser has the feature of the good and concentration of energy of monochromaticity, the laser of some wavelength to human body particularly eyes still can cause certain injury.Therefore in the occasion using laser, special safeguard procedures are needed.If use laser at infrared band, with regard to needing the apparatus be made up of strong infrared absorbing material, user is protected.
The organic compound of strong infrared Absorption is had to be commonly referred to as Infrared dyes.Through development for many years, Infrared dyes has become a class Functional dye, their chemical structure wide variety, and dithiolene metal complexes of the present invention is exactly a class wherein.Have bibliographical information, this kind of Infrared dyes can be used as the infrared absorbing material of night viewing compatible, and is making in the eye-protection glasses with infrared absorption performance, there are no relevant report.
Trace it to its cause, mainly be, existing dithiolene metal complexes or be poorly soluble in organic solvent, not there is polymerisable group (as: 1) Men Jinfeng etc. in infrared technique in molecule, 2007,29 (5), in 302-305,2) Gao Junxiong etc. in fine chemistry industry, 2011,28 (9), in 910-914 and 3) Thanh-Tuan Bui, et al, at New J.Chem., 2012, the dithiolene metal complexes reported in 36,2033-2041).
Given this, provide a kind of and for the preparation of the dithiolene metal complexes of eye-protection glasses with infrared absorption performance, the technical issues that need to address of the present invention can be become.
Summary of the invention
The base material of eye-protection glasses is generally polymkeric substance, as: polymethacrylate, polycarbonate, urethane or polystyrene and other polyolefinic mixtures etc.They itself do not have infrared absorption performance, and eye-protection glasses be made to have infrared absorbance energy, then must add the material with infrared absorption performance in above-mentioned polymkeric substance, such as, and Infrared dyes.The latter added in these polymkeric substance and generally have two kinds of modes, the first is physically added, that is, at polymers soln, Infrared dyes adds wherein by this.But as the polymkeric substance crosslinking polymerization often of eyeglass, thus common solvent can not dissolve this base polymer; It two is chemically add, that is, joined copolymerization therewith in the monomer of polymkeric substance.Obviously, if do not have polymerizable groups in Infrared dyes molecule, then this copolymerization just can not occur.
The present inventor has designed and synthesized a kind of dithiolene metal complexes of novel structure for this reason.Dithiolene metal complexes provided by the invention not only has good solubility energy in organic solvent, and copolymerization can be carried out with forming the monomer with the eye-protection glasses base material of infrared absorption performance, and gained multipolymer has good infrared absorption performance, can be used for preparing the eye-protection glasses with infrared absorption performance.
The present invention's object is, discloses a kind of dithiolene metal complexes of novel structure.Dithiolene metal complexes of the present invention is compound shown in formula I:
In formula I, R is the thiazolinyl of the thiazolinyl of straight or branched or the straight or branched of phenyl replacement, the metallic element that M comprises for VIII race in the periodic table of elements and I B race.
Another object of the present invention is, discloses a kind of purposes of above-mentioned dithiolene metal complexes, and namely compound shown in formula I is preparing the application had in the eye-protection glasses of infrared absorption performance.
Prepare the preparation method of compound shown in formula I of the present invention, comprise the steps:
(1) by zincate and corresponding halohydrocarbons reaction, the step of compound shown in preparation formula II; With
(2) step of target compound (shown in formula I compound) is prepared by compound shown in formula II.
In formula II, the definition of R is with described identical above.
Accompanying drawing explanation
Fig. 1. be compound spectral absorption curve in different organic solvents shown in formula I a;
A-acetone, b-methylene dichloride, c-toluene, d-zellon.
Fig. 2. be the spectral absorption curve of the copolymer A of compound shown in formula I a of different concns and methyl methacrylate.
Fig. 3. be compound spectral absorption curve in different organic solvents shown in formula I b;
A-acetone, b-methylene dichloride, c-toluene, d-zellon.
Fig. 4. be the spectral absorption curve of compound shown in formula I b of different concns and cinnamic multipolymer B.
Embodiment
In the present invention's preferred technical scheme, R is C
2~ C
6the C that the thiazolinyl of straight or branched or phenyl replace
2~ C
6the thiazolinyl of straight or branched;
Preferred technical scheme is that R is C further
2~ C
4the C that the thiazolinyl of straight or branched or phenyl replace
2~ C
4the thiazolinyl of straight or branched;
Preferred technical scheme is that R is further again
or
wherein Ph represents phenyl, and curve marker bit is for replacing position.
In another preferred technical scheme of the present invention, M is Ni, Pd or Au.
Shown in preparation formula I of the present invention, the method for compound, specifically comprises the steps:
(1) by zincate (shown in formula III compound) in organic solvent with containing the halohydrocarbons reaction of unsaturated double-bond, 4 are after products therefrom is purified, 5-dithio alkyl-1,3-dithiole-2-thioketones (shown in formula II compound); With
(2) 4,5-dithio alkyl-1,3-dithiole-2-thioketones (shown in formula II compound) is joined in freshly prepared sodium methylate/methyl alcohol, then add quaternary ammonium salt and divalent-metal ion reacts.Reaction terminates rear removing methyl alcohol, and resistates acetonitrile dissolves, and continues reaction, be target compound (shown in formula I compound) after product is purified after adding oxygenant.
Compound shown in the formula I of gained is mixed with monomer (as: methyl methacrylate or vinylbenzene etc. are for the preparation of the base material of eye-protection glasses), having under initiator existence condition, carry out copolyreaction, after reaction terminates, reaction solution is poured in culture dish, after solvent evaporates, obtain solid-state co-polymer (eye-protection glasses base).
Below will the present invention is described in detail by embodiment, its object is only better to understand content of the present invention.Therefore, the cited case does not limit the scope of the invention.
Embodiment 1
(1) 4,5-dithio allyl group-1,3-dithiole-2-thioketones (compound ii synthesis a)
By zincate (compound III) (8.60g, 12mmol) be added in there-necked flask with acetonitrile (100ml), be heated to backflow, drip propenyl chloride (4.59g, acetonitrile solution 60mmol), TLC follows the tracks of reaction process.After reaction terminates, cooling, filters, filter cake acetonitrile wash.Merging filtrate and washings, silica gel column chromatography (sherwood oil/methylene dichloride is eluent, 6/1, v/v) after concentrated, obtain yellow oil (5.64g), (compound ii is productive rate 84.6% a).
1H NMR(400MHz,CDCl
3)δ,ppm:5.97-5.67(m,4H),5.37-5.00(m,8H),3.64-3.26(m,8H)；ESI-MS:m/z＝278(M+).
(2) target compound (chemical compounds I synthesis a)
Compound ii a (2.78g, 10mmol) is joined in freshly prepared sodium methylate (1.35g, 25mmol)/methyl alcohol.65 DEG C of reactions, the stopped reaction (about 2.5h) when the color of reaction solution is brown color.Cool to room temperature, drips n-Bu
4nBr (3.22g, 10mmol) and NiCl
26H
2the methanol solution of O (1.19g, 5mmol), room temperature reaction 5h, decompression steams methyl alcohol, and resistates adds I after dissolving with acetonitrile (100ml)
2(3.81g, 15mmol), under room temperature, reaction is spent the night.Filter, use methyl alcohol and washed with dichloromethane respectively, merging filtrate and washings, revolve and steam solvent, and residue over silica gel column chromatography (sherwood oil/methylene dichloride is eluent, 6/1, v/v) obtains chemical compounds I a 0.86g, productive rate: 32.7%.
1H NMR(400MHz,CDCl
3)δ,ppm:6.05(ddt,J＝16.9,10.1,6.9Hz,4H),5.35(dd,J＝65.3,13.5Hz,8H),4.05(d,J＝7.0Hz,8H).MALPI-TOF MS:m/z＝525.8748(M
+).
Chemical compounds I a has higher solubleness common are in machine solvent, and wherein, at acetone, methylene dichloride, the absorption curve in toluene and zellon is shown in Fig. 1.
With the copolymerization of methyl methacrylate
Chemical compounds I a is dissolved in methylene dichloride, mix with methyl methacrylate by different mol ratios, after stirring, add initiator (such as, Diisopropyl azodicarboxylate), be warmed up to 50 DEG C, reaction 8h, be poured in culture dish, after solvent evaporates, obtain the copolymer A containing different concns, their absorption spectrum curve is shown in Fig. 2.
Embodiment 2
(1) synthesis of intermediate (compound ii b)
By zincate (compound III) (8.60g, 12mmol) be added in there-necked flask with acetonitrile (100ml), be heated to backflow, drip 3-phenyl-chlorallylene (9.15g, acetonitrile solution 60mmol), TLC follows the tracks of reaction process.After reaction terminates, cooling, filters, filter cake acetonitrile wash.Merging filtrate and washings, silica gel column chromatography (sherwood oil/methylene dichloride is eluent, 6/1, v/v) after concentrated, obtains yellow oil 8.85g (compound ii b), productive rate 85.8%.
1H NMR(400MHz,CDCl
3)δ,ppm:7.33(dd,J＝19.2,9.5Hz,8H),7.14(dd,J＝29.9,7.7Hz,8H),6.69(dd,J＝17.5,10.9Hz,4H),5.75(d,J＝17.6Hz,4H),5.27(dd,J＝10.8,5.9Hz,4H),3.94-3.80(m,8H)；ESI-MS:m/z＝430(M
+).
(2) synthesis of target compound (compoundsⅰb)
Compound ii b (4.30g, 10mmol) is joined in freshly prepared sodium methylate (1.35g, 25mmol)/methyl alcohol.65 DEG C of reactions, the stopped reaction (about 2.5h) when the color of reaction solution is brown color.Cool to room temperature, drips n-Bu
4nBr (3.22g, 10mmol) and NiCl
2˙ 6H
2the methanol solution of O (1.19g, 5mmol), room temperature reaction 5h, decompression steams methyl alcohol, and resistates adds I after dissolving with acetonitrile (100ml)
2(3.81g, 15mmol), under room temperature, reaction is spent the night.Filter, use methyl alcohol and washed with dichloromethane respectively, merging filtrate and washings, revolve and steam solvent, and residue over silica gel column chromatography (sherwood oil/methylene dichloride is eluent, 6/1, v/v), obtains 1.31g compoundsⅰb, productive rate 31.6%.
1H NMR(400MHz,CDCl
3)δ,ppm:7.31(dd,J＝16.2,10.2Hz,8H),6.71(ddd,J＝17.5,10.9,3.9Hz,4H),5.77(d,J＝17.6Hz,4H),5.28(d,J＝10.9Hz,4H),4.55(s,8H),1.32(dd,J＝17.3,14.4Hz,8H).MALPI-TOF MS:m/z＝830.0045(M
+).
Compoundsⅰb has higher solubleness common are in machine solvent, and wherein, at acetone, methylene dichloride, the absorption curve in toluene and zellon is shown in Fig. 3.
With cinnamic copolymerization
Compoundsⅰb is dissolved in tetrahydrofuran (THF), mix with vinylbenzene by different mol ratios, after stirring, add initiator (Diisopropyl azodicarboxylate), be warmed up to 60 DEG C, reaction 8h, is poured in culture dish, obtain after solvent evaporates containing different concns compoundsⅰb and cinnamic multipolymer B, their absorption spectrum curve is shown in Fig. 4.
Claims (6)
1. a dithiolene metal complexes, it is compound shown in formula I:
In formula I, R is the thiazolinyl of the thiazolinyl of straight or branched or the straight or branched of phenyl replacement, the metallic element that M comprises for VIII race in the periodic table of elements and I B race.
2. dithiolene metal complexes as claimed in claim 1, it is characterized in that, wherein R is C
2~ C
6the C that the thiazolinyl of straight or branched or phenyl replace
2~ C
6the thiazolinyl of straight or branched.
3. dithiolene metal complexes as claimed in claim 2, it is characterized in that, wherein R is C
2~ C
4the C that the thiazolinyl of straight or branched or phenyl replace
2~ C
4the thiazolinyl of straight or branched.
4. dithiolene metal complexes as claimed in claim 3, it is characterized in that, wherein R is
wherein Ph represents phenyl, and curve marker bit is for replacing position.
5. dithiolene metal complexes as claimed in claim 1, it is characterized in that, wherein M is Ni, Pd or Au.
6. as dithiolene metal complexes as described in any one in claim 1 ~ 6 is preparing the application had in the eye-protection glasses of infrared absorption performance.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424679A (en) * | 2018-04-08 | 2018-08-21 | 大连理工大学 | A kind of polymer coating with the coordination containing bimetallic of infrared optics characteristic, preparation method and applications |
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| JP2006195399A (en) * | 2004-03-09 | 2006-07-27 | Mitsubishi Chemicals Corp | Near-infrared absorption filter |
| JP2007021890A (en) * | 2005-07-15 | 2007-02-01 | Mitsubishi Chemicals Corp | Optical recording medium, coloring matter for forming its recording layer and recording method |
| CN101163771A (en) * | 2005-04-28 | 2008-04-16 | 株式会社Api | Pressure-sensitive adhesive containing near infrared absorbing coloring matter |
| JP2009023915A (en) * | 2007-07-17 | 2009-02-05 | Api Corporation | Method for producing dithiacyclopentene derivative or diselenacyclopentene derivative |
| US20100019212A1 (en) * | 2006-10-27 | 2010-01-28 | Api Corporation | Near infrared ray-absorbable dye composition, and near infrared ray-absorbable filter and adhesive agent both comprising the composition |
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2015
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Patent Citations (5)
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| JP2006195399A (en) * | 2004-03-09 | 2006-07-27 | Mitsubishi Chemicals Corp | Near-infrared absorption filter |
| CN101163771A (en) * | 2005-04-28 | 2008-04-16 | 株式会社Api | Pressure-sensitive adhesive containing near infrared absorbing coloring matter |
| JP2007021890A (en) * | 2005-07-15 | 2007-02-01 | Mitsubishi Chemicals Corp | Optical recording medium, coloring matter for forming its recording layer and recording method |
| US20100019212A1 (en) * | 2006-10-27 | 2010-01-28 | Api Corporation | Near infrared ray-absorbable dye composition, and near infrared ray-absorbable filter and adhesive agent both comprising the composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424679A (en) * | 2018-04-08 | 2018-08-21 | 大连理工大学 | A kind of polymer coating with the coordination containing bimetallic of infrared optics characteristic, preparation method and applications |
| CN108424679B (en) * | 2018-04-08 | 2020-04-07 | 大连理工大学 | Polymer coating with infrared optical characteristic and containing bimetal coordination, preparation method and application thereof |
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