CN101570475A - Solid organic magnetic compound 4-chloro bi-indene tetrone and synthetic method - Google Patents
Solid organic magnetic compound 4-chloro bi-indene tetrone and synthetic method Download PDFInfo
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Abstract
The invention discloses solid organic magnetic compound 3-chloro bi-indene tetrone and a synthetic method thereof. The invention takes 4-chloro phthalic anhydride and butane diacid as raw materials to synthesize 4-chloro bi-indene tetrone; the structural formula of the 4-chloro bi-indene tetrone is as follows; the synthetic method is as follows: 4-chloro phthalic anhydride and butane diacid are taken as raw materials to prepare an intermediate used for synthesizing 4-chloro bi-indene tetrone; and then the an intermediate is catalyzed by sodium alkoxide to synthesize the 4-chloro bi-indene tetrone. The 4-chloro bi-indene tetrone provided by the invention is the organic magnetic compound, has better magnetism function, can be applied to fields such as new generation high stored information material, separation material, light broadband microwave absorption, magnetic sensors, small loss and high frequency micro-wave commutation devices, magnetic sealing devices, magnetic shades, magnetic separation, micro-wave communication, etc.
Description
[technical field]:
The invention belongs to the organic materials synthesis technical field, particularly a kind of organic compound and synthetic method thereof with solid-state paramagnetism specific physical character.
[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]
[summary of the invention]:
The object of the invention provides a kind of novel molecular solid organic magnetic compound, 4-chlorin bi-indene tetrone and synthetic method thereof.
Organic magnetic compound 4-chloro bi-indene tetrone provided by the invention, its structural formula is:
The synthetic method of described 4-chlorin bi-indene tetrone comprises:
Synthetic route:
Concrete synthesis step is as follows:
The first, 4-chlorin bi-indene tetrone intermediate is synthetic
Thermometer is being housed, in reflux exchanger and the churned mechanically four-hole bottle, is adding 4-chloro-phthalic anhydride and Succinic Acid (mol ratio is 1: 1～2), be warming up to 210 ℃.Start stirring, (mol ratio of potassium acetate and 4-chloro-phthalic anhydride is 0.2～0.35: 1), 210 ℃ were reacted 2～4 hours to add potassium acetate, 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, boil to remove resinous impurities with ethanol, refilter, with ethanol wash elutant colourless till, drying, get little reddish yellow powder, be the intermediate that is used for synthetic 4-chlorin bi-indene tetrone.
The second, the 4-chlorin bi-indene tetrone 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 (mol ratio of intermediate and sodium methylate is 1: 2～3) was 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, with in the hydrochloric acid and water lotion, separate out the tetraketone of purple pulpous state in the water lotion, use the oil of mirbane recrystallization, obtain the acicular compound of atropurpureus, i.e. the 4-chlorin bi-indene tetrone.
The structural characterization data:
IR:(KBr, diffuse-reflectance, cm
-1) 3410.22,3059.36,1631.69,1575.5,1523.65
1H-NMR(300MHz，DMSO)：
：7.10(m，6H0，14.63(m，2H)
MS：m/z?358(M
+)
ESR test result: g=2.004.
Advantage of the present invention and positively effect:
Organic compound 4-chlorin bi-indene tetrone provided by the invention is a kind of novel organic magnetic compound, has magnetic function preferably.
Organic magnetic compound provided by the invention can be used for 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 ESR spectrogram of compound 4-chloro bi-indene tetrone.
[embodiment]:
Embodiment 1:
The first, thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, is adding 3-chloro-phthalic anhydride 30.5g (0.167mol) and Succinic Acid (being adding in 1: 1 in molar ratio), be warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of potassium acetate and 3-chloro-phthalic anhydride is 0.2: 1), 210 ℃ were reacted 2 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, little reddish yellow powder 17.6g, be the intermediate that is used for synthetic 4-chlorin bi-indene tetrone.
The second, thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, the 16.0g intermediate is being suspended 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 with in the hydrochloric acid and water lotion, is separated out the tetraketone of purple pulpous state in the water lotion, use the oil of mirbane recrystallization, obtains the acicular compound of atropurpureus, i.e. 4-chlorin bi-indene tetrone 9.8g, yield 61.3%.M.p.298 ℃ (decomposition).
Embodiment 2:
The first, thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, is adding 4-chloro-phthalic anhydride 30.5g (0.167mol) and Succinic Acid (mol ratio is 1: 1.5), be warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of potassium acetate and 3-monochloro phthalic anhydride is 0.3: 1), 210 ℃ were reacted 2 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, little reddish yellow powder 15.2g, be the intermediate that is used for synthetic 4-chlorin bi-indene tetrone.
The second, thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, the 14.0g intermediate is being suspended 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: 2.5) 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, overanxious while hot, with in the hydrochloric acid and water lotion, separate out the tetraketone of purple pulpous state in the water lotion, use the oil of mirbane recrystallization, obtain the acicular compound of atropurpureus, i.e. 4-chlorin bi-indene tetrone 8.6g, yield 61.4%.M.p.298 ℃ (decomposition).
Embodiment 3:
The first, thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, is adding 4-chloro-phthalic anhydride 30.5g (0.167mol) and Succinic Acid (mol ratio is 1: 2), be warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of potassium acetate and 3-monochloro phthalic anhydride is 0.25: 1), 210 ℃ were reacted 2 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, little reddish yellow powder 16.5g, be the intermediate that is used for synthetic 4-chlorin bi-indene tetrone.
The second, thermometer is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, the 16.0g intermediate is being suspended 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: 3) 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 with in the hydrochloric acid and water lotion, is separated out the tetraketone of purple pulpous state in the water lotion, use the oil of mirbane recrystallization, obtains the acicular compound of atropurpureus, i.e. 4-chlorin bi-indene tetrone 9.3g, yield 58.4%.M.p.298 ℃ (decomposition).
The test of 4-chlorin bi-indene tetrone ESR magnetic
Condition determination: F=9.849GHz, P=0.797mW, ST=167.772s.
The ESR spectrum parameter g=2.004 of 4-chlorin bi-indene tetrone.
. 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
Claims (2)
1, a kind of solid organic magnetic compound 4-chloro bi-indene tetrone, its structural formula is:
2, the synthetic method of the described 4-chlorin bi-indene tetrone of a kind of claim 1 comprises:
Synthetic route:
Concrete synthesis step is as follows:
The first, 4-chlorin bi-indene tetrone intermediate is synthetic
Thermometer is being housed, in reflux exchanger and the churned mechanically four-hole bottle, be that 1: 1～2 ratio adds 4-chloro-phthalic anhydride and Succinic Acid in molar ratio, be warming up to 210 ℃, start stirring, add potassium acetate, the mol ratio of potassium acetate and 4-chloro-phthalic anhydride 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 little reddish yellow powder, is the intermediate that is used for synthetic 4-chlorin bi-indene tetrone;
The second, the 4-chlorin bi-indene tetrone 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, sodium methoxide solution drips, the mol ratio of intermediate and sodium methylate is 1: 2～3, with mixed-liquor return reaction 0.5～1.5 hour, cooling was filtered, it is colourless to effluent liquid to wash the black product with dehydrated alcohol, with aqueous suspension black product and boil, filtered while hot is with in the hydrochloric acid and water lotion, separate out the tetraketone of purple pulpous state in the water lotion, use the oil of mirbane recrystallization, obtain the acicular compound of atropurpureus, i.e. the 4-chlorin bi-indene tetrone.
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Effective date of registration: 20180906 Address after: 300300 revitalization of 5-2-302 in Dongli District, Tianjin Patentee after: Chun ho Jin (Tianjin) Technology Co., Ltd. Address before: 300191 No. 263 Hongqi South Road, Tianjin, Nankai District Patentee before: Tianjin University of Technology |
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Address after: 215000 room 7b, Jinshi building, Shishan Road, high tech Zone, Suzhou, Jiangsu 054 Patentee after: Junhejin (Suzhou) Technology Co.,Ltd. Address before: 300300 revitalization of 5-2-302 in Dongli District, Tianjin Patentee before: Junhe Jin (Tianjin) Technology Co.,Ltd. |