CN101570474B - Solid organic magnetic compound 4,4'-dicloro-2, 2'- bi-indan-1,1', 3,3'- tetrone and synthetic method - Google Patents
Solid organic magnetic compound 4,4'-dicloro-2, 2'- bi-indan-1,1', 3,3'- tetrone and synthetic method Download PDFInfo
- Publication number
- CN101570474B CN101570474B CN2009101420837A CN200910142083A CN101570474B CN 101570474 B CN101570474 B CN 101570474B CN 2009101420837 A CN2009101420837 A CN 2009101420837A CN 200910142083 A CN200910142083 A CN 200910142083A CN 101570474 B CN101570474 B CN 101570474B
- Authority
- CN
- China
- Prior art keywords
- chloro
- tetraketone
- indanes
- tetrone
- magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a solid organic magnetic compound 4,4'-dichloro-2,2'-diindan-1,1',3,3'-tetrone and a synthetic method thereof. The structural formula of the 4,4'-dichloro-2,2'-diindan-1,1',3,3'-tetrone provided by the invention is as follows. The synthetic method comprises the following steps: taking 3- chlorin phthalic anhydride and butane diacid as raw materials to prepare an intermediate for synthesizing the 4,4'-dichloro-2,2'-diindan-1,1',3,3'-tetrone; and then synthesizing the 4,4'-dichloro-2,2'-diindan-1,1',3,3'-tetrone after sodium alcoholate catalysisi. The 4,4'-dichloro-2,2'-diindan-1,1',3,3'-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 cpds and compound 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 theoretical and the 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 possibly 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 very slowly.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 the scientist Ovchinnikov of the FSU in 1987
[10]Reported first Poly-BIPO
[1, and 4-bis (2,2,6,6-tetramethyl4-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 cpds that people is recognized contain N, O 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, 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3,3 '-tetraketone and compound method thereof.
Organic magnetic compound 4,4 '-two chloro-2,2 '-two indanes-1 provided by the invention, 1 ', 3,3 '-tetraketone, its structural formula is:
Described 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the compound method of 3 '-tetraketone comprises:
Synthetic route:
Concrete synthesis step is following:
The second, 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3,3 '-tetraketone midbody synthetic
TM is being housed, in reflux exchanger and the churned mechanically four-hole bottle, is adding 3-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 3-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 is boiled to remove resinous impurities with ethanol.Refilter, with ethanol wash elutant colourless till, drying, little reddish yellow powder, be and be used for synthetic 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the midbody of 3 '-tetraketone.
The second, 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3,3 '-tetraketone synthetic
TM is being housed, in reflux exchanger and the churned mechanically four-hole bottle, midbody is being suspended with methyl alcohol; Be warming up to 60 ℃; Under agitation, the sodium methoxide solution that drips (mol ratio of midbody and sodium methylate is 1: 2～3) was with mixed-liquor return reaction 0.5～1.5 hour.Cooling is filtered, and it is colourless to wash black product to effluent with absolute ethyl 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. 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3,3 '-tetraketone.
The structural characterization data:
IR: (KBr, diffuse-reflectance, cm
-1) 3442.24,3066.18,1626.80,1574.81,1514.41
MS：m/z358(M
+)
1H-NMR(300MHz，DMSO)δ：7.25(m，6H)，14.13(s，2H)。
ESR test result: g=2.004.
Advantage of the present invention and positively effect:
Organic cpds 4,4 '-two chloro-2,2 '-two indenes provided by the invention sea 1,1 ', 3,3 '-tetraketone 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 magneticshielding, magnetic separation, microwave communication.
[description of drawings]
Fig. 1 is a compound 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the ESR spectrogram of 3 '-tetraketone.
[embodiment]:
Embodiment 1:
The first, TM 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 (mol ratio is 1: 1), 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 16.0g, be and be used for synthetic 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the midbody of 3 '-tetraketone.
The second, TM is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, the 16.0g midbody is being suspended with methyl alcohol; Be warming up to 60 ℃; Under agitation, the sodium methoxide solution that drips (mol ratio of midbody and sodium methylate is 1: 2) was with mixed-liquor return reaction 1 hour.Cooling is filtered, and it is colourless to wash black product to effluent with absolute ethyl 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; Obtain the acicular compound of atropurpureus, i.e. 4,4 '-two chloro-, 2,2 '-two indanes-1; 1 ', 3,3 '-tetraketone 9.6g, yield 60.3%.M.p.298 ℃ (decomposition).
Embodiment 2:
The first, TM 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 (mol ratio is 1: 1.5), be warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of potassium acetate and 3-chloro-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 18.0g, be and be used for synthetic 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the midbody of 3 '-tetraketone.
The second, TM is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, the 18.0g midbody is being suspended with methyl alcohol; Be warming up to 60 ℃; Under fierce the stirring, the sodium methoxide solution that drips fast (mol ratio of midbody and sodium methylate is 1: 2.5) was with mixed-liquor return reaction 1 hour.Cooling is filtered, and it is colourless to wash black product to effluent with absolute ethyl 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; Obtain the acicular compound of atropurpureus, i.e. 4,4 '-two chloro-, 2,2 '-two indanes-1; 1 ', 3,3 '-tetraketone 12.8g, yield 71.2%.M.p.298 ℃ (decomposition).
Embodiment 3:
The first, TM 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 (mol ratio is 1: 2), be warming up to 210 ℃.Start stirring, add potassium acetate (mol ratio of potassium acetate and 3-chloro-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 17.5g, be and be used for synthetic 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the midbody of 3 '-tetraketone.
The second, TM is being housed, in reflux exchanger and the churned mechanically 250mL four-hole bottle, the 16.0g midbody is being suspended with methyl alcohol; Be warming up to 60 ℃; Under agitation, the sodium methoxide solution that drips (mol ratio of midbody and sodium methylate is 1: 2.8) was with mixed-liquor return reaction 1 hour.Cooling is filtered, and it is colourless to wash black product to effluent with absolute ethyl 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; Obtain the acicular compound of atropurpureus, i.e. 4,4 '-two chloro-, 2,2 '-two indanes-1; 1 ', 3,3 '-tetraketone 8.9g, yield 55.6%.M.p.298 ℃ (decomposition).
4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the ESR magnetic test of 3 '-tetraketone
Condition determination: F=9.849GHz, P=2.002mW, ST=83.886s.
4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3, the ESR spectrum parameter g=2.004 of 3 '-tetraketone.
. reference
[1]Nakamuta，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.Commm.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.-plant solid organic magnetic compound 4,4 '-two chloro-2,2 '-two indanes-1,1 ', 3,3 '-tetraketone, its structural formula is:
2. described 4,4 '-two chloro-of claim 12,2 '-two indanes-1,1 ', 3, the compound method of 3 '-tetraketone is characterized in that comprising:
Synthetic route:
Concrete synthesis step is following:
The first, 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3,3 '-tetraketone midbody synthetic
TM is being housed, and in reflux exchanger and the churned mechanically four-hole bottle, is that 1: 1～2 ratio adds 3-chloro-phthalic anhydride and Succinic Acid in molar ratio, is warming up to 210 ℃, starts stirring; Add potassium acetate, the mol ratio of potassium acetate and 3-chloro-phthalic anhydride is 0.2～0.35: 1,210 ℃ of reaction 2～4 hours, is cooled to 100 ℃ then; Add hot water and import water vapour, form broken particle, filter, use the hot water wash product up to reaction product; Drying is boiled to remove resinous impurities with ethanol, refilter, with ethanol wash elutant colourless till; Drying gets little reddish yellow powder, is to be used for synthetic 4,4 '-two chloro-2; 2 '-two indanes-1,1 ', 3, the midbody of 3 '-tetraketone;
The second, 4,4 '-two chloro-, 2,2 '-two indanes-1,1 ', 3,3 '-tetraketone synthetic
TM is being housed, in reflux exchanger and the churned mechanically four-hole bottle, midbody is being suspended with methyl alcohol, be warming up to 60 ℃, under agitation; The sodium methoxide solution that drips, the mol ratio of midbody and sodium methylate is 1: 2～3, with mixed-liquor return reaction 0.5～1.5 hour, cooling was filtered; It is colourless to wash black product to effluent with absolute ethyl alcohol, and 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, obtain the acicular compound of atropurpureus, be i.e. 4,4 '-two chloro-2; 2 '-two indanes-1,1 ', 3,3 '-tetraketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101420837A CN101570474B (en) | 2008-05-30 | 2009-05-27 | Solid organic magnetic compound 4,4'-dicloro-2, 2'- bi-indan-1,1', 3,3'- tetrone and synthetic method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810053336 | 2008-05-30 | ||
| CN200810053336.9 | 2008-05-30 | ||
| CN2009101420837A CN101570474B (en) | 2008-05-30 | 2009-05-27 | Solid organic magnetic compound 4,4'-dicloro-2, 2'- bi-indan-1,1', 3,3'- tetrone and synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101570474A CN101570474A (en) | 2009-11-04 |
| CN101570474B true CN101570474B (en) | 2012-05-02 |
Family
ID=41229976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101420837A Expired - Fee Related CN101570474B (en) | 2008-05-30 | 2009-05-27 | Solid organic magnetic compound 4,4'-dicloro-2, 2'- bi-indan-1,1', 3,3'- tetrone and synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101570474B (en) |
-
2009
- 2009-05-27 CN CN2009101420837A patent/CN101570474B/en not_active Expired - Fee Related
Non-Patent Citations (5)
| Title |
|---|
| JP平4-180604A 1992.06.26 |
| Vladimir Khodorkovsky et al.A new strong electron acceptor.The resurrection of 2,2"-biindanylidene-1,3,1",3"-tetraone.《Tetrahedron letters》.1994,第35卷(第18期),2955-2958. * |
| Xu Li et al.Synthesis,structure,crystalline-state photochromism and photoinduced behavior of [2,2"-bi-1H-indene]-1,1"-dione-3,3"-dihydroxy-3,3"-diisobutyl.《Journal of Molecular Structure》.2005,第748卷161-164. * |
| Xu Li.Photochromism and crystal structure of 3,3"-dimethyl-3,3"-dihydroxy-5,5"-dimethyl-2,2"-bi-1H-indanylidene-1,1"-dione.《Journal of chemical research》.2008,191-192. * |
| Yong Chen et al.Synthesis,crystal structures,and photochromic properties of 6,6"or 7,7"or 6,7"-dimethyl-[2,2"-bi-1H-indene]-3,3"-diethyl-3,3"-dihydroxy-1,1"-diones.《Tetrahedron》.2007,第63卷4319-4327. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101570474A (en) | 2009-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI750333B (en) | Sensitizing dye, sensitizing dye composition for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar bettery | |
| WO2017041642A1 (en) | Compound based on meta-linked bihydrazinoazine structure and preparation method and use thereof | |
| CN111393452B (en) | Asymmetric thieno-indole nuclear small molecule receptor material and preparation method thereof | |
| CN101570527B (en) | Solid magnetism and fluorescence organic compound 3-chlorin bi-indene isolactone and synthetic method | |
| CN101591317B (en) | Solid magnetic and fluorescent organic compound of 4-chlorobiindenylisolactone and synthesis method thereof | |
| CN101570526B (en) | Solid magnetism and fluorescence organic compound 4-methyl bi-indene isolactone and synthetic method | |
| CN112409323A (en) | Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal | |
| Yang et al. | A sulfur-containing hetero-octulene: Synthesis, host–guest properties, and transistor applications | |
| CN105541850B (en) | A kind of phthalocyanine-like compound and its synthetic method and application | |
| CN101570474B (en) | Solid organic magnetic compound 4,4'-dicloro-2, 2'- bi-indan-1,1', 3,3'- tetrone and synthetic method | |
| CN101570475B (en) | Solid organic magnetic compound 4-chloro bi-indene tetrone and synthetic method | |
| Meti et al. | Unveiling the photophysical and morphological properties of an acidochromic thiophene flanked dipyrrolopyrazine-based chromophore for optoelectronic application | |
| Rajakumar et al. | Pyreno-chalcone dendrimers as an additive in the redox couple of dye-sensitized solar cells | |
| JP2009269905A (en) | Method of synthesizing electroconductive polymer simple substance | |
| CN108892969B (en) | 3, 5-position non-aryl substituted R-azaBODIPY fluorescent dye and preparation method thereof | |
| TWI731165B (en) | Sensitizing dye, sensitizing dye for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell | |
| Nakano et al. | Synthesis and intramolecular magnetic interaction of triphenylamine derivatives with nitronyl nitroxide radicals | |
| Wang et al. | Synthesis and Characterization of Planar Five‐Ring‐Fused Dithiophene‐dione | |
| Ren et al. | Synthesis and properties of novel spirobifluorene-cored dendrimers | |
| CN101585824B (en) | Solid magnetic and fluorescent organic compound tetrachloro biindyl isolactone and its synthetic method | |
| CN106673976B (en) | A kind of preparation method of Alpha-hydroxy cyclopentadecanone | |
| Tan et al. | Syntheses, characterizations and electrochemical properties of mesomorphic 4-(4′-alkoxy-(1, 1′-biphenyl)-4-oxy) butane-1-sulfonic acids | |
| CN113637023B (en) | Asymmetric indole derivative nuclear small molecule receptor material and preparation method thereof | |
| CN103664647A (en) | 2,3-diamino-7-bromo-9,9'-dialkylfluorene and preparation method thereof | |
| CN115093412B (en) | Organic thermoelectric functional material based on end-group electron-withdrawing base benzene ring derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120502 Termination date: 20150527 |
|
| EXPY | Termination of patent right or utility model |