CN101585824A - Solid magnetic and fluorescent organic compound tetrachloro biindyl isolactone and its synthetic method - Google Patents
Solid magnetic and fluorescent organic compound tetrachloro biindyl isolactone and its synthetic method Download PDFInfo
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- CN101585824A CN101585824A CNA2009101420964A CN200910142096A CN101585824A CN 101585824 A CN101585824 A CN 101585824A CN A2009101420964 A CNA2009101420964 A CN A2009101420964A CN 200910142096 A CN200910142096 A CN 200910142096A CN 101585824 A CN101585824 A CN 101585824A
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Abstract
A solid magnetic and fluorescent double function organic compound tetrachloro biindyl isolactone and its synthetic method. The invention uses the tetrachlorophthalic anhydride and the succinic acid as raw materials for synthesizing the tetrachloro biindyl isolactone. The structural formula is as follows. The synthesizing method comprises following steps: mixing the tetrachlorophthalic anhydride and the succinic acid, heating reaction, taking the potassium acetate as a catalyst, preparing the intermediate for synthesizing the tetrachloro biindyl isolactone, catalyzing by sodium alcoholate, synthesizing the tetrachloro biindyl isolactone. The tetrachloro biindyl isolactone is a solid magnetic and fluorescent organic compound, has the double functions of fluorescence and paramagnetism, can be applied in the fields of fluorescence labeling and recognition, novel high stored information material, isolation material, light wideband microwave absorbing agent, magnetic sensor, low loss high-frequency microwave communication device, magnetic seal device, magnetic shield, magnetic separation and microwave communication.
Description
[technical field]:
The invention belongs to the organic materials synthesis technical field, particularly a kind of have fluorescence and bifunctional organic compound of magnetic and a synthetic method thereof.
[background technology]:
Organic magnet is the frontier branch of science of a multidisciplinary intersection, it relates to subjects such as organic and inorganic, organo-metallic, polymkeric substance, physical chemistry, Condensed Matter Physics, belongs to main research and has magnetic, photoconduction, electricity and the design of the molecular system of specific physical character, synthetic and application such as lead
[1]Emerging research field---the molecular solid (Molecular solid) of multidisciplinary intersection.For a long time, people think that an organic/inorganic substance just has above these character, and organism then is considered to diamagnetic material or electrical insulator.Up to recently, all proved in the theoretical and test some special organic materials through overdoping or with other organic or inorganic ionic bond after, can show magnetic or change conductor into even superconductor.Phase at the beginning of the sixties in last century, MeConnell
[2]Proposition is encouraging people to make unremitting effort for seeking such system based on the theory prophesy that the ferro-magnetic of molecular system may exist.At present, this field relates to organic semiconductor, organic photoconductor, organic conductor and superconductor, conductive polymers, organic non linear optical material, new-type functional material such as Organic Ferromagnet and relevant electronic processes.Compare with other materials research, though the research of Organic Ferromagnet is started late, researchdevelopment has in recent years fully shown the development potentiality in this field.
First molecule ferro-magnetic is by ferrocene [Fe (Cp
*)
2] charge-transfer complex that forms with TCNE (TCNE)
[3]: [Fe (η
5-C
5Me
5)
2]
+[TCNE]
-, be that people such as Miller was in report in 1986; Meanwhile, Kahn
[4]Reported MnCu (pbaOH) (H
2O)
3Have ferromegnetism, this has just announced the ferromagnetic birth of molecule.In recent years, the research of magneticsubstance has obtained challenging progress, Verdaguer again
[5,6]With people such as Epstein
[7]Reported the V (TCNE) of Tc respectively up to 340K
21/2 (CH
2Cl
2) and [Cr (CN) of 500K
6]
Q-V
P+The molecule ferro-magnetic.
Phase at the beginning of the sixties in last century, scientists has just begun the theoretical investigation of Organic Ferromagnet, but progress is very slow.1963, McConnell
[2]The possibility of Organic Ferromagnet has been proposed.Nineteen sixty-eight Mataga
[8], Ovchinnikov in 1978
[9]Proved its possibility again theoretically.Up to USSR (Union of Soviet Socialist Republics) scientist Ovchinnikov in 1987
[10]Reported first Poly-BIPO[1, and 4-bis (2,2,6,6-tetramethyl-4-piperidyl-1-oxyl)-Butadiyne] had since macroscopical ferromegnetism, the research of organic magnet is just really come out.1991, first Organic Ferromagnet based on C, H, O, four kinds of elements of N just was synthesized out
[11], the organic compound that people is recognized contain N, O free radical also is the ferromagnetic a kind of effective ways of preparation molecule
[12]
Traditional biological label method comprises radioisotope method and fluorescence labeling method.Radio isotope can produce radiation to organism, environment is polluted, and radio isotope all has the transformation period of himself, signal can be more and more a little less than, so this method is abandoned by people now gradually.And the signal to noise ratio height, the fluorescence labeling technology that sensitivity is good has been widely used in biological and medical aspect, plays an important role in fields, life science forward position such as biochip, protein analysis, dna sequencing, fluoroimmunoassay, fluidic cell measurement, clinical analysis of diagnosis and treatments
[13-14]Therefore, novel fluorescent compound is synthetic significant.
[summary of the invention]:
The object of the invention provides a kind of novel molecular solid paramagnetism and fluorescent dual-function organic compound, tetrachloro bi-indene isolactone and synthetic method thereof.
Molecular solid paramagnetism provided by the invention and fluorescent dual-function organic compound tetrachloro biindyl isolactone, its structural formula is:
The synthetic method of above-mentioned tetrachloro bi-indene isolactone comprises:
Synthetic route:
Concrete synthesis step is as follows:
Synthesizing of first, fourth chlorin bi-indene isolactone intermediate
Thermometer is being housed, in reflux exchanger and the churned mechanically four-hole bottle, add tetrachlorophthalic tetrachlorophthalic anhydrid and Succinic Acid (mol ratio is 1: 1～2), be warming up to 210 ℃, start stirring, (mol ratio of potassium acetate and tetrachlorophthalic tetrachlorophthalic anhydrid is 0.2～0.35: 1) to add potassium acetate, 210 ℃ were reacted 2～4 hours, were cooled to 100 ℃ then, added hot water and also imported water vapour, form broken particle up to reaction product, filter, use the hot water wash product, drying, boil to remove resinous impurities with ethanol, refilter, with ethanol wash elutant colourless till, drying, get the mustard yellow powder, be the intermediate that is used for synthetic tetrachloro bi-indene isolactone.
The second, the tetrachloro bi-indene isolactone is synthetic
Thermometer is being housed, in reflux exchanger and the churned mechanically four-hole bottle, the intermediate that the last step was obtained suspends with methyl alcohol, be warming up to 60 ℃, under agitation, the sodium methoxide solution that drips, the mol ratio of intermediate and sodium methylate was 1: 2～3, with mixed-liquor return reaction 0.5～1.5 hour, cooling, filter, it is colourless to effluent liquid to wash the black product with dehydrated alcohol, with aqueous suspension black product and boil, filtered while hot, it is colourless to effluent liquid to continue the water flush cake, obtains red solid, i.e. the tetrachloro bi-indene isolactone.
The structural characterization data:
1HNMR：δ(ppm)14.32(s，2H)
IR:(KBr, diffuse-reflectance, cm
-1) 3507.75,2948.38,1632.09,1579.26,1522.93,1467.20,1381.90,1345.53
MS：m/z?342(M
+)，300，286，242(100)，214，179，142，107，91，44
ESR test result: g=2.004.
Advantage of the present invention and positively effect:
Organic compound tetrachloro biindyl isolactone provided by the invention is a kind of novel solid magnetic and fluorescence organic compound, has fluorescence and paramagnetism is difunctional.
Solid magnetic provided by the invention and fluorescence organic compound can be used for fluorescent mark, identification field; And organo-metallic material, can be applied to high canned data material of new generation, isolated material, lightweight wide-band microwave absorption agent, magneticsensor, low-loss high-frequency microwave communication device, magnetic seal device, fields such as magnetic shielding, magnetic separation, microwave communication.
[description of drawings]
Fig. 1 is the fluorogram (in the methyl alcohol) of tetrachloro bi-indene isolactone;
Fig. 2 is the ESR spectrogram of tetrachloro bi-indene isolactone.
[embodiment]:
Embodiment 1:
Thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, is adding tetrachlorophthalic tetrachlorophthalic anhydrid 28.6g (0.100mol) and Succinic Acid (mol ratio is 1: 1), be warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of potassium acetate and tetrachlorophthalic tetrachlorophthalic anhydrid is 0.2: 1), 210 ℃ were reacted 2.5 hours.Be cooled to 100 ℃ then, add hot water and import water vapour.Form broken particle up to reaction product, filter, use the hot water wash product, drying is boiled to remove resinous impurities with ethanol.Refilter, with ethanol wash elutant colourless till, drying, mustard yellow powder 21.0g, be the intermediate that is used for synthetic tetrachloro bi-indene isolactone.
Thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, 15.0g is upward being gone on foot the intermediate that obtains suspend with methyl alcohol, be warming up to 60 ℃, under agitation, the sodium methoxide solution that drips (mol ratio of intermediate and sodium methylate is 1: 2) was with mixed-liquor return reaction 1 hour.Cooling is filtered, and it is colourless to effluent liquid to wash the black product with dehydrated alcohol.With aqueous suspension black product and boil, filtered while hot, it is colourless to elutant to continue the water flush cake, obtains red solid, i.e. tetrachloro bi-indene isolactone 2.3g.Yield 15.3%.m.p.＞300℃。
Embodiment 2:
Thermometer is being housed, and reflux exchanger and machine subtract in the 250mL four-hole bottle of stirring, add tetrachlorophthalic tetrachlorophthalic anhydrid 45.2g (0.267mol) and Succinic Acid (mol ratio is 1: 1.5), are warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of tetrachlorophthalic tetrachlorophthalic anhydrid and potassium acetate is 1: 0.3), 210 ℃ were reacted 2.5 hours.Be cooled to 100 ℃ then, add hot water and import water vapour.Form broken particle up to reaction product, filter, use the hot water wash product, drying is boiled to remove resinous impurities with ethanol.Refilter, with ethanol wash elutant colourless till, drying, mustard yellow powder 18.0g, be the intermediate that is used for synthetic tetrachloro bi-indene isolactone.
Thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, 16.0g is upward being gone on foot the intermediate that obtains suspend with methyl alcohol, be warming up to 60 ℃, under agitation, the sodium methoxide solution that drips (mol ratio of intermediate and sodium methylate is 1: 2) was with mixed-liquor return reaction 0.5 hour.Cooling is filtered, and it is colourless to effluent liquid to wash the black product with dehydrated alcohol.With aqueous suspension black product and boil, filtered while hot, it is colourless to elutant to continue the water flush cake, obtains red solid, i.e. tetrachloro bi-indene isolactone 3.2g.Yield 20.0%.m.p.＞300℃。
Embodiment 3:
Thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, is adding tetrachlorophthalic tetrachlorophthalic anhydrid 45.2g (0.267mol) and Succinic Acid (mol ratio is 1: 2), be warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of tetrachlorophthalic tetrachlorophthalic anhydrid and potassium acetate is 1: 0.3), 210 ℃ were reacted 2.5 hours.Be cooled to 100 ℃ then, add hot water and import water vapour.Form broken particle up to reaction product, filter, use the hot water wash product, drying is boiled to remove resinous impurities with ethanol.Refilter, with ethanol wash elutant colourless till, drying, mustard yellow powder 16.0g, be the intermediate that is used for synthetic tetrachloro bi-indene isolactone.
Thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, 15.0g is upward being gone on foot the intermediate that obtains suspend with methyl alcohol, be warming up to 60 ℃, under agitation, the sodium methoxide solution that drips (mol ratio of intermediate and sodium methylate is 1: 2) was with mixed-liquor return reaction 1.5 hours.Cooling is filtered, and it is colourless to effluent liquid to wash the black product with dehydrated alcohol.With aqueous suspension black product and boil, filtered while hot, it is colourless to elutant to continue the water flush cake, obtains red solid, i.e. tetrachloro bi-indene isolactone 1.8g.Yield 12.0%.m.p.＞300℃。
Photoluminescent property is measured
The fluorescent characteristic of chemical combination tetrachloro biindyl isolactone (in the methyl alcohol) sees Table 1:
The fluorescent characteristic of table 1, chemical combination tetrachloro biindyl isolactone
The test of ESR magnetic
Test condition: Hm=0.8mT, P=1mw, AMP=65db, τ c=0.1s, Sweep time=5min
The ESR spectrum parameter g=2.004 of tetrachloro bi-indene isolactone.
Reference
[1]Nakamura，T.et?al.Nature?1998，394：159
[2]McConnell，H.M.J.Chem.Phys.1963，39：1910
[3]Miller，J.S.et?al.J.Chem.Soc.Chem.Commun.1986，1026
[4]Rei，Y.et?al.J.Am.Chem.Soc.1986，108：7428
[5]Ferlays，et?al.Nature?1995，378：701
[6]Mallah.T.et?al.Science?1993，262：1554
[7]Manriquez，J.M.et?al.Science?1991，252：1415
[8]Mataga，N.Theor.Chim.Acta.1968，10：372
[9]Ovchinnikov，A.A.Theor.Chim.Acta.1978，47：297
[10]Korshak，Y.V.et?al.Nature?1987，326：370
[11]Turek，P.et?al.Chem.Phys.Lett.1991，180：327
[12]Li，Y.L.et?al.Chem.Phys.Lett.1997，265：361
[13]Schobel?U，Egelhaaf?H?J，.Brechl?A.Bioconjugate?Chem.，1999，10(6)：1107-1114
[14]Mujumbdar?S?R，Mujumbdar?R?B，Waggoner?C?M.Bioconjugate?Chem.，1996，7(3)：356-362。
Claims (2)
1, a kind of solid magnetic and fluorescence organic compound tetrachloro biindyl isolactone, its structural formula is:
2, the synthetic method of the described tetrachloro bi-indene isolactone of a kind of claim 1 comprises:
Synthetic route:
Concrete synthesis step is as follows:
Synthesizing of first, fourth chlorin bi-indene isolactone intermediate
Thermometer is being housed, in reflux exchanger and the churned mechanically four-hole bottle, be that 1: 1～2 ratio adds tetrachlorophthalic tetrachlorophthalic anhydrid and Succinic Acid in molar ratio, be warming up to 210 ℃, start stirring, add potassium acetate, the mol ratio of potassium acetate and tetrachlorophthalic tetrachlorophthalic anhydrid is 0.2～0.35: 1,210 ℃ of reaction 2～4 hours, be cooled to 100 ℃ then, add hot water and import water vapour, form broken particle, filter up to reaction product, use the hot water wash product, drying is boiled to remove resinous impurities with ethanol, refilters, with ethanol wash elutant colourless till, drying gets the mustard yellow powder, is the intermediate that is used for synthetic tetrachloro bi-indene isolactone;
The second, the tetrachloro bi-indene isolactone is synthetic
Thermometer is being housed, in reflux exchanger and the churned mechanically four-hole bottle, intermediate is suspended with methyl alcohol, be warming up to 60 ℃, under agitation, the sodium methoxide solution that drips, the mol ratio of intermediate and sodium methylate is 1: 2～3, with mixed-liquor return reaction 0.5～1.5 hour, cooling is filtered, and it is colourless to effluent liquid to wash the black product with dehydrated alcohol, with aqueous suspension black product and boil, filtered while hot continues the water flush cake, boils with concentrated hydrochloric acid that thoroughly to remove lixiviating colourless to elutant again, obtain red fine acicular crystal, i.e. the tetrachloro bi-indene isolactone.
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