CN104193613A - 1,3,5-tris(2-carboxyvinyl)benzene and preparation method thereof - Google Patents

1,3,5-tris(2-carboxyvinyl)benzene and preparation method thereof Download PDF

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CN104193613A
CN104193613A CN201410370780.9A CN201410370780A CN104193613A CN 104193613 A CN104193613 A CN 104193613A CN 201410370780 A CN201410370780 A CN 201410370780A CN 104193613 A CN104193613 A CN 104193613A
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benzene
catalyzer
synthetic
preparation
carboxy vinyl
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CN104193613B (en
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江国庆
姜国民
顾学芳
田澍
詹文毅
颜瑞
郭小青
郭向向
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Nantong University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention discloses 1,3,5-tris(2-carboxyvinyl)benzene and a preparation method thereof. The preparation method comprises the steps of synthesizing 1,3,5-phenyltricarboxaldehyde, synthesizing 1,3,5-tris(2-carboxyvinyl)benzene and the like. The preparation method disclosed by the invention is simple and convenient, high in yield and easily operated.

Description

1,3,5 ?three (2 ?carboxy vinyl) benzene and preparation method thereof
Technical field
The present invention relates to a kind of 1,3,5 ?three (2 ?carboxy vinyl) benzene and preparation method thereof.
Background technology
Metal-organic coordination polymer, claim again metal-organic framework (Metal-organic Fr ameworks), to be connected with transition metal and the mesh skeleton that forms by the organic ligand containing oxygen or nitrogen, spatially form one dimension, two dimension or the three-dimensional ligand polymer without limit structure, it is the novel cellular solid of a class, structure is various, excellent performance, at selective catalysis, molecular recognition, gas adsorption, ion-exchange, ultra-high purity parting material, biological conductive material, photoelectric material, novel semiconductor material, the field such as magneticsubstance and chip development has shown tempting application prospect.
Along with the day by day continuous deterioration of deficient and ecotope of the traditional energy such as oil and coal, Hydrogen Energy is considered to optimal novel energy, and the development and utilization of while Hydrogen Energy relates to preparation, storage, transportation and the application of hydrogen.The storage hydrogen mode adopting at present mainly contains four kinds: high-pressure hydrogen storing, liquefaction hydrogen storage, hydride hydrogen-storing and adsorption hydrogen-storing.Every kind of method has relative merits separately, and for example the advantage of traditional high-pressure hydrogen storing maximum is simple to operate, and energy consumption is little, but also has two large shortcomings: one is dangerous, and the 2nd, higher to hydrogen tank requirement of strength; Liquefaction hydrogen storage mode is defectiveness also: the one, and liquefaction of hydrogen consumed energy is large, and the 2nd, to the heat-insulating property of hydrogen container, require high; Hydride hydrogen-storing, the density of unit volume storage hydrogen is high, can equal or exceed liquid hydrogen, storage efficiency is high, and storage hydrogen pressure is not high, safer, do not need complicated container, and can obtain highly purified hydrogen, so this is a kind of more promising storage hydrogen mode, but the subject matter that this storage hydrogen mode faces is to be difficult to obtain high hydrogen storage and the good hydrogen dynamic performance that stores simultaneously; At present, for storing up the sorbent material of hydrogen, mainly contain: molecular sieve, general gac, gac and new adsorbent that specific surface area is high.
MOFs has the duct that special topological framework, inside have specific dimensions and shape, MOFs is different from inorganic molecule sieve, its duct is jointly to consist of metal ion and organic ligand, organic molecule and organic reaction are had to larger activity and selectivity, and the preparation metal ion of MOFs and the range of choice of organic ligand are very large.MOFs, as a kind of porous material of extremely-low density, can store the fuel gas such as a large amount of methane and hydrogen, for the vehicles of new generation provide energy storage means easily, will in new energy materials, play an important role.
During preparation MOFs, modal organic ligand is aromatic derivant carboxylate, and this class part itself has lot of advantages: (1) contains a plurality of bridged portions, has multiple coordination mode with metal ion; (2), according to the degree of deprotonation, part itself can be simultaneously as hydrogen bond receptor with to body; (3) rigid structure of the stability of multiple tooth chelating coordinate bond and aromatic carboxylic acid part has guaranteed the stable of complex structure after adsorption and desorption.
Summary of the invention
The object of the present invention is to provide a kind of new aromatic derivant carboxylate---1,3,5-tri-(2-carboxy vinyl) benzene and preparation method thereof.
Technical solution of the present invention is:
A kind of 1,3,5 ?three (2 ?carboxy vinyl) benzene, it is characterized in that: chemical structural formula is:
A kind of 1,3,5 ?the preparation method of three (2 ?carboxy vinyl) benzene, it is characterized in that: comprise the following steps:
(1) 1,3,5 ?benzene trioxin synthetic
(1) preparation of catalyzer
By Kui Lin ?add in the xylene solution of sulphur Pd/BaSO4 catalyzer, the reaction of anhydrous dimethyl benzene make Quinoline ?the Pd/BaSO4 catalyzer that partly poisons of S, synthetic for next step;
(2) synthetic
With 1,3,5 ?benzene three formyl chlorides are raw material, and the Pd/BaSO4 catalyzer that Quinoline ?S partly poisons is catalyzer, and hydrogenating reduction synthesizes 1,3,5 ?benzene trioxins, and reaction formula is as follows:
Obtain reacting rear mixture;
(3) separating-purifying
After the reaction that (2) step is obtained mixture separation purify 1,3,5 ?benzene trioxin sterling;
(2) 1,3,5 ?three (2 ?carboxy vinyl) benzene synthetic
With 1,3,5 ?benzene trioxin and propanedioic acid be raw material, pyridine and hexahydropyridine be catalyzer synthetic 1,3,5 ?three (2 ?carboxy vinyl) benzene, reaction formula is as follows:
In step (1), in Pd/BaSO4 catalyzer, the mass content of Pd is 5%.
The inventive method is easy, and yield is high, easy to operate.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is 1,3,5-tri-(2-carboxy vinyl) benzene FT-IR spectrogram.
Fig. 2 is 1,3,5-tri-(2-carboxy vinyl) benzene 1hNMR spectrogram.
Fig. 3 is 1,3,5-tri-(2-carboxy vinyl) benzene LC-MS spectrogram.
Embodiment
Embodiment 1:1,3,5-benzene trioxin synthetic
(1) preparation of catalyzer
By after 6.0g sulphur and 1.0g quinoline backflow 5h, with anhydrous dimethyl benzene (sodium Metal 99.5 backflow 72h, until the indicator benzophenone adding becomes bluish voilet), be diluted to 70mL; make the xylene solution of quinoline-sulphur; concentration is 0.1g/mL, and argon shield is standby.In 50mL flask, add 2.5g Pd/BaSO4 (wherein the mass content of Pd is 5%) catalyzer; the xylene solution of the above-mentioned quinoline-sulphur of 1mL; anhydrous dimethyl benzene 20mL; stir; argon shield, backflow 1h, is cooled to room temperature; make the Pd/BaSO4 catalyzer that Quinoline-S partly poisons, synthetic for next step.
(2) synthetic
With 1,3,5-benzene, three formyl chlorides, for raw material, the Pd/BaSO4 catalyzer that Quinoline-S partly poisons is catalyzer, and hydrogenating reduction synthesizes 1,3,5-benzene trioxin, and reaction formula is as follows:
By 25.0g (0.094mol) 1,3, Pd/BaSO4 catalyzer, 250mL dimethylbenzene that all Quinoline-S that 5-benzene three formyl chlorides, (1) step newly prepare partly poison add in 1L autoclave, vacuumize nitrogen replacement air 3 times, hydrogen exchange nitrogen 3 times, finally H2 pressure is fixed on to 1.0MPa, strong magnetic machinery stirs, and rotating speed is 800r/min, temperature of reaction maintains 150 ℃, TLC trace analysis.After reaction 4h, be cooled to below 100 ℃, emit a large amount of hydrogen chloride gas, then hydrogen make-up, pressure is 1.0MPa, stirs, and is warming up to 150 ℃, continues reaction 4h, stops heating, spends the night and is cooled to room temperature.Vacuumize, nitrogen replacement hydrogen 3 times, opens reactor, takes out the rear mixture of reaction.
(3) separating-purifying
Mixture after (2) step reaction is filtered, by the dimethylbenzene flush cake twice of 60mL heat, collect filtrate, and with 100mL distilled water wash three times, separatory, organic phase anhydrous sodium sulfate drying, solvent xylene is removed in underpressure distillation, obtain 1,3,5-benzene trioxin crude product.With 200-300 order silica gel, make sorbent material, normal hexane and ethyl acetate (3:1, v/v) are eluent, crude product is carried out to column chromatography separating purification, obtain 1,3,5-benzene trioxin sterling 8.19g (0.0505mol), yield 53.8%, fusing point: 154.5-158.8 ℃.
FT-IR (KBr compressing tablet) is (cm-1): 2874,1695,1595,1464,1379,1355,1241,1141,966,866,652.
1H?NMR(CD3Cl,δ)：10.21(s,3H),8.65(s,3H)。
Embodiment 21,3,5-tri-(2-carboxy vinyl) benzene synthetic
With 1,3,5-benzene trioxin and propanedioic acid, for raw material, pyridine and hexahydropyridine are synthetic 1,3,5-tri-(2-carboxy vinyl) benzene of catalyzer, and reaction formula is as follows:
In 250mL there-necked flask, add 18.72g (0.18mol) propanedioic acid, 8.1g (0.05mol) 1, 3, 5-benzene trioxin, 60mL (0.72mol) pyridine and 0.5mL (0.005mol) hexahydropyridine, stir, be heated to 110 ℃ of left and right, back flow reaction 5h, reaction mixture is cooled to room temperature, pour the hydrochloric acid of 100mL3mol/L into, separate out white precipitate, ageing is spent the night, filter, wash filter cake to filtrate with water and be neutral, dry, obtain white solid, crude product obtains target product 1 by re-crystallizing in ethyl acetate, 3, 5-tri-(2-carboxy vinyl) benzene 12.3g (0.0427mol), yield 85.4%, fusing point: 266.1-268.5 ℃.
FT-IR (KBr compressing tablet) is (cm-1): 3426,3069,1692,1636,1442,1292,1168,983,856,588.
1H?NMR(DMSO-d6,，δ)：6.61(d，3H)，7.58(s，3H),8.06(d，3H),11.86(s，3H)。
LC-M?S(m/e):calcd?for?C15H12O6:288.06,found289.0。Ultimate analysis, calculated value: C62.50%, H4.20%; Measured value: C62.34%, H4.25%.

Claims (3)

1. one kind 1,3,5 ?tri-(2 ?carboxy vinyl) benzene, is characterized in that: chemical structural formula is:
2. one kind 1,3, the preparation method of 5 ?tri-(2 ?carboxy vinyl) benzene, is characterized in that: comprise the following steps:
(1) 1,3,5 ?benzene trioxin synthetic
(1) preparation of catalyzer
By Kui Lin ?add in the xylene solution of sulphur Pd/BaSO4 catalyzer, the reaction of anhydrous dimethyl benzene make Quinoline ?the Pd/BaSO4 catalyzer that partly poisons of S, synthetic for next step;
(2) synthetic
With 1,3,5 ?benzene three formyl chlorides are raw material, and the Pd/BaSO4 catalyzer that Quinoline ?S partly poisons is catalyzer, and hydrogenating reduction synthesizes 1,3,5 ?benzene trioxins, and reaction formula is as follows:
Obtain reacting rear mixture;
(3) separating-purifying
After the reaction that (2) step is obtained mixture separation purify 1,3,5 ?benzene trioxin sterling;
(2) 1,3,5 ?three (2 ?carboxy vinyl) benzene synthetic
With 1,3,5 ?benzene trioxin and propanedioic acid be raw material, pyridine and hexahydropyridine be catalyzer synthetic 1,3,5 ?three (2 ?carboxy vinyl) benzene, reaction formula is as follows:
According to claim 21,3,5 ?the preparation method of three (2 ?carboxy vinyl) benzene, it is characterized in that: in step (1), in Pd/BaSO4 catalyzer, the mass content of Pd is 5%.
CN201410370780.9A 2014-07-30 2014-07-30 1,3,5 three (2 carboxy vinyl) benzene and preparation method thereof Expired - Fee Related CN104193613B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112645805A (en) * 2020-12-23 2021-04-13 北京理工大学 Method for preparing trimesic aldehyde from Wenlenbo amide

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
F.EFFENBERGER UND W. KURTZ: "《Synthese mehrfach cyclopropyl-substituierter Benzolez》", 《CHEM.BER.》 *
F.EFFENBERGER UND W. KURTZ: "《Synthese mehrfach cyclopropyl-substituierter Benzolez》", 《CHEM.BER.》, vol. 106, 31 December 1973 (1973-12-31), pages 511 - 524 *
RIED UND KÖNIGSTEIN: "《Über das 1.3.5-Triformyl-benzol (Benzol-trialdehyd-(1.3.5)》", 《 CHEM.BER.》 *
RIED UND KöNIGSTEIN: "《Über das 1.3.5-Triformyl-benzol (Benzol-trialdehyd-(1.3.5)》", 《 CHEM.BER.》, vol. 92, 31 December 1959 (1959-12-31), pages 2532 - 2542 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112645805A (en) * 2020-12-23 2021-04-13 北京理工大学 Method for preparing trimesic aldehyde from Wenlenbo amide

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