CN107118214B - A kind of synthetic method of compound - Google Patents
A kind of synthetic method of compound Download PDFInfo
- Publication number
- CN107118214B CN107118214B CN201710331664.XA CN201710331664A CN107118214B CN 107118214 B CN107118214 B CN 107118214B CN 201710331664 A CN201710331664 A CN 201710331664A CN 107118214 B CN107118214 B CN 107118214B
- Authority
- CN
- China
- Prior art keywords
- tetracarboxylic acid
- nitro
- compound
- reaction
- solution
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
Abstract
A kind of synthetic method of compound, the invention discloses a kind of 1- rosickyite alcohol radicals -3,4:9, and the synthetic method of 10- tetracarboxylic acid diimide, steps are as follows: by 1- nitro -3,4;9,10- tetracarboxylic acid diimides and potassium carbonate mixing are dissolved in polar organic solvent, agitation and dropping propanethiol, solution after reaction is added dropwise in the hydrochloric acid solution that concentration is 2moL/L, precipitating is precipitated by room temperature reaction 0.5-1.0 hours, filtering, distillation water washing, it is dry, purify to obtain product.Synthesising method reacting condition of the invention is mild, and reaction step is simple, easily-controllable, and obtained products collection efficiency is higher.
Description
Technical field
The present invention relates to a kind of synthetic methods of compound, belong to technical field of organic synthesis.
Background technique
Imide derivative has good photo and thermal stability, high fluorescence quantum yield, unique redox
Performance and photoelectric property, to be widely used in liquid crystal material, photoelectric material, organic solar batteries, organic effect crystal
The fields such as pipe and light emitting diode are a kind of generally acknowledged organic dyestuff with high utility value.To acid imide chemical combination
Object performs the derivatization, and mainly synthesizes different compounds by modifying two methods of its amide position and gulf position to realize.Both
Influence of the position for diimide derivative has very big difference.Amide position mainly influences the dissolution of diimide derivative
Degree, gulf position carry out rosickyite alcoholization can directly affect nuclear electron arrangement, thus influence diimide derivative absorption and
Fluorescence property is a kind of important derivatization method.
It can be by by 1- nitro -3,4 currently, carrying out rosickyite alcoholization to acid imide gulf position;Two acyl of 9,10- tetrabasic carboxylic acid
Imines and potassium carbonate mixing are dissolved in chloroform solvent, agitation and dropping propanethiol, and the lower heating reaction of argon gas protection obtains for 10 hours, are produced
Rate is 95 (2012) 450-454 of 35%(X. Kong et al. Dyes and Pigments).Reaction time is long, yield compared with
It is low.Therefore, it is particularly significant to abundant acid imide synthesis chemistry that other convenience and high-efficiencies, mild controllable derivatization method are sought.
Summary of the invention
For the above-mentioned prior art, the object of the present invention is to provide a kind of synthetic methods of compound.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of compound 1- rosickyite alcohol radical -3,4:9,10- tetracarboxylic acid diimide, structural formula are as follows:
The synthetic method of a kind of compound, which is characterized in that steps are as follows:
By 1- nitro -3,4;9,10- tetracarboxylic acid diimides and potassium carbonate mixing are dissolved in polar organic solvent, are stirred
Propanethiol is added dropwise, reacts at room temperature 0.5-1.0 hours, the solution after reaction is added dropwise in the hydrochloric acid solution that concentration is 2moL/L,
Precipitating is precipitated, water washing is distilled in filtering, and it is dry, purify to obtain 1- rosickyite alcohol radical -3,4:9,10- tetracarboxylic acid diimide.
A kind of synthetic method of the compound, characterized in that the dosage of the potassium carbonate is every gram of nitro -3 1-,
4;9,10- tetracarboxylic acid diimide is with 0.5-2 grams.
A kind of synthetic method of the compound, characterized in that the dosage of the propanethiol is every gram of nitro -3 1-,
4;9,10- tetracarboxylic acid diimide is with 20-60 milliliters.
The synthetic method of a kind of compound, characterized in that the dosage of the polar organic solvent is every gram of 1-
Nitro -3,4;9,10- tetracarboxylic acid diimide is with 40-200 milliliters.
The synthetic method of a kind of compound, characterized in that the polar organic solvent is N- methylpyrrole
Alkanone.
The synthetic method of a kind of compound, characterized in that purifying is using with methylene chloride and petroleum ether
Mixed solvent is mobile phase, silica gel column chromatography purifying.
The compound of the present invention 1- rosickyite alcohol radical -3,4:9,10- tetracarboxylic acid diimide synthetic route is as follows:
1- rosickyite alcohol radical -3,4:9 synthesized by the method for the present invention, 10- tetracarboxylic acid diimide, at 1 of gulf position
Rosickyite alcohol radical auxochrome is introduced, the electronic structure of 3,4:9,10- tetracarboxylic acid diimide is effectively changed, has adjusted it
Photophysical property enhances solubility in organic solvent, organic solar batteries, in terms of have it is potential
Application value
The beneficial effects of the present invention are: the synthesising method reacting condition of the compound is mild, reaction step is simple, easily-controllable,
Obtained products collection efficiency is higher, and yield is up to 60% or more.
Detailed description of the invention
Fig. 1 is the mass spectrum of compound 1- rosickyite alcohol radical -3,4:9,10- tetracarboxylic acid diimide prepared by embodiment 1；
Fig. 2 is the nuclear-magnetism hydrogen of compound 1- rosickyite alcohol radical -3,4:9,10- tetracarboxylic acid diimide prepared by embodiment 1
Spectrum.
Specific embodiment
The present invention is further illustrated by the following examples.
Embodiment 1
In 50 mL flasks, 1- nitro -3,4 is added;9,10- tetracarboxylic acid diimide (0.2 g, 0.34 mmol),
Potassium carbonate (0.2 g) and 20 mL N-Methyl pyrrolidones, sonic oscillation make it dissolve, are stirred at room temperature down, and 8.0 mL third are added dropwise
Mercaptan, TLC tracking reaction, reacts at room temperature 0.5 hour, stops reaction, the solution after reaction, which is added dropwise to 100 ml concentration, is
In the hydrochloric acid solution of 2moL/L, precipitating is precipitated, vacuum filtration distills water washing (50 ml × 3), and 70 DEG C are dried in vacuo 5 hours.
Crude product is isolated and purified by silica gel column chromatography (methylene chloride: petroleum ether=4:1), obtains 1- rosickyite alcohol radical -3,4:9,10- tetra-
Imide 130mg, yield 61%.Fig. 1 is the mass spectrogram of compound manufactured in the present embodiment, and Fig. 2 is that the present invention is implemented
The hydrogen nuclear magnetic resonance spectrogram of the compound of example preparation.
Embodiment 2
In 50 mL flasks, 1- nitro -3,4 is added;9,10- tetracarboxylic acid diimide (0.2 g, 0.34 mmol),
Potassium carbonate (120 mg) and 20mL N-Methyl pyrrolidone, sonic oscillation make it dissolve, are stirred at room temperature down, and 8.0 mL third are added dropwise
Mercaptan, TLC tracking reaction, reacts at room temperature 1 hour, stops reaction, and it is 2moL/ that the solution after reaction, which is added dropwise to 100 ml concentration,
In the hydrochloric acid solution of L, precipitating is precipitated, vacuum filtration distills water washing (50 ml × 3), and 70 DEG C are dried in vacuo 5 hours.Crude product
It is isolated and purified by silica gel column chromatography (methylene chloride: petroleum ether=4:1), obtains 1- rosickyite alcohol radical -3,4:9,10- tetrabasic carboxylic acid two
Acid imide 132mg, yield 62%.
Embodiment 3
In 50 mL flasks, 1- nitro -3,4 is added;9,10- tetracarboxylic acid diimide (0.1 g, 0.34 mmol),
Potassium carbonate (0.1g) and 15mL N-Methyl pyrrolidone, sonic oscillation make it dissolve, are stirred at room temperature down, and 5.0 mL rosickyite are added dropwise
Alcohol, TLC tracking reaction, reacts at room temperature 0.5 hour, stops reaction, and it is 2moL/ that the solution after reaction, which is added dropwise to 100 ml concentration,
In the hydrochloric acid solution of L, precipitating is precipitated, vacuum filtration distills water washing (50 ml × 3), and 70 DEG C are dried in vacuo 5 hours.Crude product
It is isolated and purified by silica gel column chromatography (methylene chloride: petroleum ether=4:1), obtains 1- rosickyite alcohol radical -3,4:9,10- tetrabasic carboxylic acid two
Acid imide 66mg, yield 62%.
Claims (1)
1. a kind of compound synthesis method, it is characterised in that:
A.1- nitro -3,4;9,10- tetracarboxylic acid diimide and potassium carbonate mixing are dissolved in polar organic solvent N- methylpyrrole
In alkanone, agitation and dropping propanethiol is reacted at room temperature 0.5-1.0 hours;
B. the solution after reacting is added dropwise in the hydrochloric acid solution that concentration is 2mol/L, and precipitating is precipitated, and filtering, distillation water washing are done
It is dry;
C. methylene chloride and petroleum ether mixed solvent are mobile phase, and silica gel column chromatography purifies to obtain 1- rosickyite alcohol radical -3,4:9,
10- tetracarboxylic acid diimide；
Every gram of 1- nitro -3,4 of dosage of potassium carbonate;For 9,10- tetracarboxylic acid diimides with 0.5-2 grams, the dosage of propanethiol is every
Gram 1- nitro -3,4;With 20-60 milliliters, the dosage of organic solvent N-Methyl pyrrolidone is 9,10- tetracarboxylic acid diimides
Every gram of 1- nitro -3,4;9,10- tetracarboxylic acid diimide is with 40-200 milliliters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710331664.XA CN107118214B (en) | 2017-05-12 | 2017-05-12 | A kind of synthetic method of compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710331664.XA CN107118214B (en) | 2017-05-12 | 2017-05-12 | A kind of synthetic method of compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107118214A CN107118214A (en) | 2017-09-01 |
| CN107118214B true CN107118214B (en) | 2019-05-03 |
Family
ID=59726893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710331664.XA Expired - Fee Related CN107118214B (en) | 2017-05-12 | 2017-05-12 | A kind of synthetic method of compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107118214B (en) |
-
2017
- 2017-05-12 CN CN201710331664.XA patent/CN107118214B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| Aromatic nitro substitution reaction between 4-nitro-N-n-butyl-1,8-naphthalimide and n-heptanethiol in water–methanol binary mixtures;Eduardo Rezende Triboni et al.;《J. Phys. Org. Chem.》;20081224;第22卷;第703–708页 |
| Facile synthesis and replacement reactions of mono-substituted perylene bisimide dyes;Xiangxue Kong et al.;《Dyes and Pigments》;20120519;第95卷;第450-454页 |
| Preparation of 1,8-naphthalimides as Candidate Fluorescent Probes of Hypoxic Cells;Richard et al.;《J.Heterocyclic Chem》;19851231;第22卷;第1567-1572页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107118214A (en) | 2017-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110437172A (en) | A kind of 3,7- bis- replaces phenoxazine analog derivative and preparation method thereof | |
| CN103613599B (en) | A kind of position, gulf of 3,4:9,10-perylene tetracarboxylic acid diimides becomes ring synthetic method | |
| CN101423522A (en) | Diperylene-3,4,6,7:12,13,15,16-octocarboxylic tetraimides compounds and production method thereof | |
| CN104387388A (en) | Novel method for synthetizing gulf-site n-heterocyclic 3,4:9,10-perylene tetracarboxylic acid diimide | |
| CN104649923B (en) | 1-Amino-12-hydroxy-3,4: 9,10-perylene n-butyl tetracarboxylate and synthesis method thereof | |
| CN107118214B (en) | A kind of synthetic method of compound | |
| CN105294721A (en) | Synthetic method and micrometer wire preparation method of perylene bisimide derivative | |
| CN106146496A (en) | A kind of gulf district cyclization synthetic method of double imide derivative | |
| CN110499040A (en) | A kind of gulf area replaces π-extension class dyestuff and preparation method thereof | |
| CN105837588B (en) | A kind of monoamides analog derivative of the embedding oxygen hexa-member heterocycle 3,4,9,10- tetracarboxylic acid diimides in gulf position and its preparation method and application | |
| CN109824691A (en) | Liquid-crystal compounds and its preparation based on cyclopentadiene 1,4-Dithiapentalene -4- ketone | |
| CN104974173B (en) | A kind of gulf embedding pentatomic sulphur heterocycle in position and hexa-atomic oxa- ring 3,4:The preparation method of 9,10 perylene tetracarboxylic acid N-butyls | |
| CN110143970B (en) | Sulfur-rich dinaphthalene diimide derivative and preparation method and application thereof | |
| CN102876318B (en) | Fluorene acid ester fluorescent material and preparation method thereof | |
| CN107098904A (en) | Application of 1,7, the Yi Zhong perylenes gulf containing nitro perylene diimides derivative and its in ammonia detection | |
| CN104744290B (en) | A kind of synthetic method of imide analog compounds | |
| CN112174962A (en) | Synthesis method of benzo [ e ] pyridylimidazo [4,5-g ] isoindole-1, 3(2H) -diketone compound | |
| CN108623594B (en) | A kind of loop coil aromatic condensed ring imide analog compounds and preparation method thereof | |
| CN113754606A (en) | Phenoxazinediamine derivatives and/or phenothiazine diamine derivatives and preparation method thereof | |
| CN106831816B (en) | 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 | |
| CN108863832B (en) | Preparation method of N-aryl amide compound | |
| CN107043384B (en) | Two furans [3,2-c:2 ', 3 '-i] [1,10] phenanthroline class compound and preparation method thereof | |
| CN106883242B (en) | A kind of preparation method of the embedding hexa-atomic oxa- ring diphenol generation -3,4,9,10- tetracarboxylic acid diimide in gulf position | |
| CN108191903B (en) | Method for synthesizing coronadimide and derivative thereof based on perylene diimide | |
| WO2020202177A1 (en) | Stable solvent-free charge transfer liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190503 Termination date: 20200512 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |