CN103613599A - Bay-site cyclization synthetic method of 3, 4:9, 10-perylenetetracarboxylic bisimide - Google Patents
Bay-site cyclization synthetic method of 3, 4:9, 10-perylenetetracarboxylic bisimide Download PDFInfo
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- CN103613599A CN103613599A CN201310652963.5A CN201310652963A CN103613599A CN 103613599 A CN103613599 A CN 103613599A CN 201310652963 A CN201310652963 A CN 201310652963A CN 103613599 A CN103613599 A CN 103613599A
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- tetracarboxylic acid
- perylene tetracarboxylic
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- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/22—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains four or more hetero rings
Abstract
The invention relates to a bay-site cyclization synthetic method of 3, 4:9, 10-perylenetetracarboxylic bisimide. The method comprises the following steps: dissolving bay-site nitrified 3, 4:9, 10-perylenetetracarboxylic bisimide and a compound which can form carbanions in a polar aprotic organic solvent; adding an alkaline matter; stirring and reacting for 0.5-5 hours in a temperature range of 0-40 DEG C; dropwise adding the reacted liquid into diluted hydrochloric acid; separating out precipitates; and filtering, washing and drying to obtain the product. The method provided by the invention guarantees the planar structure of perylenetetracarboxylic bisimide to the maximum extent, and is mild in reaction condition and simple in reaction step. The obtained product is higher in yield which is basically over 50%, and the higher yield is over 80%.
Description
Technical field
The present invention relates to a kind of novel 3,4:9, the synthetic method of position, the gulf annulation of 10-perylene tetracarboxylic acid diimides, belongs to technical field of organic synthesis.
Background technology
Perylene is that derivative is the compound that a class has plane aromatic structure, has excellent thermostability, light stability, chemical stability and good dyeing behavior.Since Kardo is since sending out existing perylene tetracarboxylic acid diimides compounds in 1913, this compounds is widely used in dyestuffs industries and coatings industry always.Along with the developmental research of photoelectric material and widespread use ， perylene based compound rely on its good photoelectric characteristic, be more and more subject to people's attention.Therefore the research of the functionalization derivatize of ， Dui perylene based compound becomes particularly important.The main derivative reaction of Mu Qian perylene based compound is substitution reaction, but the structural distortion of inevitable Dai Lai perylene based compound, thereby destroy its planarity.The unique method that keeps its planarity is in position, gulf, to form six-membered ring structure, at present generally take transition metal-catalyzed cross-coupling to form new " carbon-to-carbon " key, this reaction requires to carry out under oxygen free condition, or under illumination condition, carry out fragrant cyclisation, two kinds of methods all form larger aromatic structure and make solvability variation and reduce synthetic value.
Summary of the invention
The object of this invention is to provide a kind of 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, it has, and synthesis step is simple, raw material is easy to get, productive rate advantages of higher.
The present invention adopts following technical scheme:
A kind of 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, comprises that step is as follows:
By gulf nitrated in position 3,4:9,10-perylene tetracarboxylic acid diimides is dissolved in polar non-proton organic solvent with the compound that can form carbanion, add alkaline matter, stirring reaction 0.5～5h in 0～40 ℃ of temperature range, reacted liquid is splashed in dilute hydrochloric acid, separate out precipitation, filtration, washing, the dry product that to obtain; Described gulf nitrated in position 3,4:9,10-perylene tetracarboxylic acid diimides is 1-nitro-3,4:9,10-perylene tetracarboxylic acid diimides, 1,6-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides or 1,7-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides, the described compound that can form carbanion is ethyl cyanoacetate, methyl aceto acetate, diethyl malonate, fluorenes, 2,7-dibromo fluorenes or 2-nitropropane.
Described gulf nitrated in position 3,4:9, the consumption molar ratio of 10-perylene tetracarboxylic acid diimides, the compound that can form carbanion, alkaline matter is 1:2～10:2～20, gulf nitrated in position 3,4:9, the amount ratio of 10-perylene tetracarboxylic acid diimides and polar non-proton organic solvent is every gram of gulf nitrated in position 3,4:9, solvent 20～100mL for 10-perylene tetracarboxylic acid diimides.Preferred proportion is gulf nitrated in position 3,4:9, the consumption molar ratio of 10-perylene tetracarboxylic acid diimides, the compound that can form carbanion, alkaline matter is 1:3～5:4～6, gulf nitrated in position 3,4:9, the amount ratio of 10-perylene tetracarboxylic acid diimides and polar non-proton organic solvent is every gram of gulf nitrated in position 3,4:9, solvent 40～50mL for 10-perylene tetracarboxylic acid diimides.
Described 3,4:9,10-perylene tetracarboxylic acid diimides, is to buy acquisition by market, for example this biochemical technology company limited of Tianjin Skien.
Described 1-nitro-3,4:9,10-perylene tetracarboxylic acid diimides 1,6-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides, 1,7-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides, can pass through 3,4:9, and 10-perylene tetracarboxylic acid diimides is synthetic in mode described in document.Described document, Langhals H, Kirner S.Novel fluorescent dyes by the extension of the core of perylenetetracarboxylic bisimides[J] .European Journal of Organic Chemistry, 2000,2000 (2): 365-380.
Described gulf nitrated in position 3,4:9,10-perylene tetracarboxylic acid diimides and the described preferred 1-of the compound that can form carbanion nitro-3,4:9,10-perylene tetracarboxylic acid diimides is combined with nitropropane.
Described alkaline matter is alkali-metal inorganic or organic bases, the weak base such as the mineral alkali of preferred lithium, sodium, potassium, caesium and carbonate thereof, acetate, formate.
Described polar non-proton organic solvent is methyl-sulphoxide, DMF, pyridine, quinoline, tetrahydrofuran (THF), dioxane or N-Methyl pyrrolidone.
The product that the present invention obtains is one-sided or bilateral 3,4:9, position, 10-perylene tetracarboxylic acid diimides gulf oxa-six-membered cyclic structural compounds.
Synthetic route (with 1,7-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides is example):
Note: R is any alkyl.R
1, R
2for forming the counter structure of carbanion compound.
The invention provides a kind of novel 3,4:9, position, the gulf annulation method of 10-perylene tetracarboxylic acid diimides, with gulf nitrated in position 3,4:9,10-perylene tetracarboxylic acid diimides is raw material, with under alkaline condition, can form carbanion compound and react in polar non-proton organic solvent, form one-sided or bilateral 3,4:9, position, 10-perylene tetracarboxylic acid diimides gulf oxa-six-membered cyclic structural compounds.This structure guarantees the two dimensional structure of perylene tetracarboxylic acid diimides to greatest extent, enriches the derivatization method of perylene tetracarboxylic acid diimides.
The invention has the beneficial effects as follows:
(1), based on 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides novel " carbon-to-carbon " key forms reaction.
(2) hexa-atomic one-tenth ring structure guarantees the two dimensional structure of perylene tetracarboxylic acid diimides to greatest extent, and has avoided substituted radical steric hindrance Dao Zhi perylene planar distortion.
(3) reaction conditions is gentle, and reactions steps is simple;
(4) products collection efficiency obtaining is higher, substantially more than 50%, high more than 80%.
Accompanying drawing explanation
The nucleus magnetic hydrogen spectrum of Fig. 1 product A;
The mass spectrum of Fig. 2 product A;
The nucleus magnetic hydrogen spectrum of Fig. 3 product B;
The mass spectrum of Fig. 4 product B;
The nucleus magnetic hydrogen spectrum of Fig. 5 product C;
The mass spectrum of Fig. 6 product C.
Embodiment
Below in conjunction with embodiment, further illustrate.
Embodiment 1
Get 600 milligrams of N, N '-dicyclohexyl-1-nitro-3,4:9,10-perylene tetracarboxylic acid diimides, 0.35 milliliter of diethyl malonate and 415 milligrams of salt of wormwood are dissolved in 30 milliliters of N-Methyl pyrrolidone, stirring at room, react 3 hours, reaction solution is splashed in the dilute hydrochloric acid of 100 milliliters of 2mol/L, separate out precipitation, suction filtration, wash 3 times, dry.Thick product carries out silica gel column chromatography, and leacheate is methylene dichloride: ethyl acetate=20:1.Obtain 580 milligrams of product A (structure is shown in shown in accompanying drawing 1,2), productive rate 80%.
Get 600 milligrams of N, N '-dicyclohexyl-1-nitro-3,4:9,10-perylene tetracarboxylic acid diimides, 650 milligram 2,7-dibromo fluorenes and 415 milligrams of sodium carbonate are dissolved in 30 milliliters of dioxane, react 5 hours, cooling, reaction solution is splashed in the dilute hydrochloric acid of 100 milliliters of 2mol/L, separate out precipitation, suction filtration, washes 3 times, dries.Thick product carries out silica gel column chromatography, and leacheate is methylene dichloride.Obtain 490 milligrams of product B (structure is shown in shown in accompanying drawing 3,4), productive rate 55%.
Embodiment 3
Get 645 milligrams of N, N '-dicyclohexyl-1,6-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides, 0.4 milliliter of 2-nitropropane and 830 milligrams of potassium acetates are dissolved in 30 milliliters of N, N '-N,N-DIMETHYLACETAMIDE, be heated to 60 ℃, react 2.5 hours, cooling, reaction solution is splashed in the dilute hydrochloric acid of 100 milliliters of 2mol/L, separate out precipitation, suction filtration, washes 3 times, dries.Thick product carries out silica gel column chromatography, and leacheate is methylene dichloride.Obtain 540 milligrams of product C (structure is shown in shown in accompanying drawing 5,6), productive rate 65%.
Claims (6)
1. one kind 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, it is characterized in that, comprises that step is as follows:
By gulf nitrated in position 3,4:9,10-perylene tetracarboxylic acid diimides is dissolved in polar non-proton organic solvent with the compound that can form carbanion, add alkaline matter, stirring reaction 0.5～5h in 0～40 ℃ of temperature range, reacted liquid is splashed in dilute hydrochloric acid, separate out precipitation, filtration, washing, the dry product that to obtain; Described gulf nitrated in position 3,4:9,10-perylene tetracarboxylic acid diimides is 1-nitro-3,4:9,10-perylene tetracarboxylic acid diimides, 1,6-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides or 1,7-dinitrobenzene-3,4:9,10-perylene tetracarboxylic acid diimides, the described compound that can form carbanion is ethyl cyanoacetate, methyl aceto acetate, diethyl malonate, fluorenes, 2,7-dibromo fluorenes or 2-nitropropane.
2. according to claim 1 a kind of 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, it is characterized in that, described gulf nitrated in position 3,4:9, the consumption molar ratio of 10-perylene tetracarboxylic acid diimides, the compound that can form carbanion, alkaline matter is 1:2～10:2～20, gulf nitrated in position 3,4:9, the amount ratio of 10-perylene tetracarboxylic acid diimides and polar non-proton organic solvent is every gram of gulf nitrated in position 3,4:9, solvent 20～100mL for 10-perylene tetracarboxylic acid diimides.
3. according to claim 2 a kind of 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, it is characterized in that, gulf nitrated in position 3,4:9, the consumption molar ratio of 10-perylene tetracarboxylic acid diimides, the compound that can form carbanion, alkaline matter is 1:3～5:4～6, gulf nitrated in position 3,4:9, the amount ratio of 10-perylene tetracarboxylic acid diimides and polar non-proton organic solvent is every gram of gulf nitrated in position 3,4:9, solvent 40～50mL for 10-perylene tetracarboxylic acid diimides.
4. according to claim 1 a kind of 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, it is characterized in that, described gulf nitrated in position 3,4:9,10-perylene tetracarboxylic acid diimides and the described compound that can form carbanion select 1-nitro-3,4:9,10-perylene tetracarboxylic acid diimides is combined with nitropropane.
5. according to claim 1 a kind of 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, it is characterized in that, and described alkaline matter is alkali-metal inorganic or organic bases.
6. according to claim 1 a kind of 3,4:9, the position, gulf of 10-perylene tetracarboxylic acid diimides becomes ring synthetic method, it is characterized in that, described polar non-proton organic solvent is methyl-sulphoxide, DMF, pyridine, quinoline, tetrahydrofuran (THF), dioxane or N-Methyl pyrrolidone.
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Cited By (6)
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| CN104152137A (en) * | 2014-05-06 | 2014-11-19 | 上海大学 | Fluorine-perylene bisimide molecule internal-energy transferring fluorescence split compound and preparation method thereof |
| CN104945346A (en) * | 2015-06-19 | 2015-09-30 | 山东师范大学 | Bay-position oxygen-intercalation aza-heptatomic ring 3, 4:9, 10-perylene tetracarboxylic acid butyl acetate and synthesis method thereof |
| CN104974173A (en) * | 2015-06-08 | 2015-10-14 | 山东师范大学 | Preparation method of bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene tetracarboxylic n-butyl acrylate |
| CN106350060A (en) * | 2015-07-17 | 2017-01-25 | 济南大学 | Reactive pH molecular probe as well as preparation method and application thereof |
| CN106831816A (en) * | 2017-02-27 | 2017-06-13 | 山东师范大学 | A kind of gulf position embedding hexa-atomic thia ring and the hexa-atomic perylene tetracarboxylic acid diimides of oxa- ring 3,4,9,10 and preparation method thereof |
| CN106883242A (en) * | 2017-04-11 | 2017-06-23 | 山东师范大学 | A kind of preparation method of embedding 3,4,9,10 perylene tetracarboxylic acid diimides of hexa-atomic oxa- ring diphenol generation in gulf position |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152137A (en) * | 2014-05-06 | 2014-11-19 | 上海大学 | Fluorine-perylene bisimide molecule internal-energy transferring fluorescence split compound and preparation method thereof |
| CN104974173A (en) * | 2015-06-08 | 2015-10-14 | 山东师范大学 | Preparation method of bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene tetracarboxylic n-butyl acrylate |
| CN104945346A (en) * | 2015-06-19 | 2015-09-30 | 山东师范大学 | Bay-position oxygen-intercalation aza-heptatomic ring 3, 4:9, 10-perylene tetracarboxylic acid butyl acetate and synthesis method thereof |
| CN104945346B (en) * | 2015-06-19 | 2017-03-22 | 山东师范大学 | Bay-position oxygen-intercalation aza-heptatomic ring 3, 4, 9, 10-perylene tetracarboxylic acid butyl acetate and synthesis method thereof |
| CN106350060A (en) * | 2015-07-17 | 2017-01-25 | 济南大学 | Reactive pH molecular probe as well as preparation method and application thereof |
| CN106350060B (en) * | 2015-07-17 | 2018-08-17 | 济南大学 | A kind of response type pH value molecular probe and preparation method and purposes |
| CN106831816A (en) * | 2017-02-27 | 2017-06-13 | 山东师范大学 | A kind of gulf position embedding hexa-atomic thia ring and the hexa-atomic perylene tetracarboxylic acid diimides of oxa- ring 3,4,9,10 and preparation method thereof |
| CN106831816B (en) * | 2017-02-27 | 2019-02-19 | 山东师范大学 | A kind of gulf position embedding hexa-atomic thia ring and hexa-atomic oxa- ring -3,4,9,10- tetracarboxylic acid diimide and preparation method thereof |
| CN106883242A (en) * | 2017-04-11 | 2017-06-23 | 山东师范大学 | A kind of preparation method of embedding 3,4,9,10 perylene tetracarboxylic acid diimides of hexa-atomic oxa- ring diphenol generation in gulf position |
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