CN102617317B

CN102617317B - Method for synthesizing pyrene-4,5,9,10-tetralone

Info

Publication number: CN102617317B
Application number: CN 201210039839
Authority: CN
Inventors: 莫越奇
Original assignee: South China University of Technology SCUT
Current assignee: South China University of Technology SCUT
Priority date: 2012-02-21
Filing date: 2012-02-21
Publication date: 2013-12-25
Anticipated expiration: 2032-02-21
Also published as: CN102617317A

Abstract

The invention discloses a method for synthesizing pyrene-4,5,9,10-tetralone. The method includes the steps: (1) performing coupling reaction of 2,6-dioctyl phthalate methyl ester-1-bromobenzene and copper powder in organic solvents N and N-dimethylformamide to synthesize 2,2',6,6'-tetramethyl methyl formate biphenyl; (2) refluxing the 2,2',6,6'-tetramethyl methyl formate biphenyl and metal sodium in toluene for 2-4 hours in nitrogen atmosphere, cooling the 2,2',6,6'-tetramethyl methyl formate biphenyl and the metal sodium, washing the 2,2',6,6'-tetramethyl methyl formate biphenyl and the metal sodium after removing sodium blocks, combining organic phases and adding ethanol to ensure complete consumption of the metal sodium; and adding acid for acidizing, adding double salicylamide ethyl cobalt and methanol and performing reaction in oxygen atmosphere to obtain the pyrene-4,5,9,10-tetralone. The method has the advantages that 1) used reagents are low in cost and wide in source; 2) the synthesis process is reliable and conditions are moderate; and 3) the conversion rate of all reaction is extremely high, and products are easily purified.

Description

A kind of synthetic pyrene-4,5,9, the method for 10-tetraketone

Technical field

The invention belongs to fine chemical product, especially a kind of synthetic pyrene-4,5,9, the method for 10-tetraketone (pyrene tetraketone).

Background technology

Pyrene-4,5,9, the 10-tetraketone also is called for short the pyrene tetraketone, is a kind of important fine chemical product, is important source material and the intermediate of synthetic pyrene analog derivative and other fused ring compounds.For example, with pyrene-4,5,9, the 10-tetraketone is the reactions such as raw material and O-Phenylene Diamine, can obtain Nano graphite banded thing (nano-ribbon) ((a) Wasserfallen, the D. of solubility; Kastler, M.; Pisula, W.; Hofer, W.A.; Fogel, Y.; Wang, Z.H.; Mullen, K.J.Am.Chem.Soc.2006,128,1334. (b) Fogel, Y; Zhi, L.J.; Rouhanipour, A.; Andrienko, D.; Rader, H.J.; Mullen, K.Macromolecules 2009,42,6878.), conjugate property due to this class material structure, thereby its energy transmission charge, stimulated luminescence can or may be applied on many electronics or opto-electronic device, as polymer LED, photovoltaic cell, field effect transistor etc.The derivative of pyrene also is widely used in biological detection and chemical probing, pyrene-4,5,9 wherein, and the 10-tetraketone can be used as important raw material.

At present synthetic pyrene-4,5,9, the 10-tetraketone mainly contains three methods (seeing Fig. 1): 1) with ruthenium trichloride catalysis sodium periodate oxidation pyrene, prepare (Hu, J.; Zhang, D.; Harris, F.W.J.Org.Chem.2005,70,707.), the characteristics of this route are that step is short, but must use expensive noble ruthenium, productive rate only 35%; 2) first synthesize pyrene-4, the 5-diketone, then with the oxygenant oxidations such as chromium trioxide (Stille, J.K.; Mainen, E.L.Macromolecules 1968,1,36.), this route is because stepwise reaction, and productive rate is very low, and only 15%, almost nobody adopts at present; 3) oxidation pyrene-4,5,9,10-tetra-phenol prepare (Wasserfallen, D.; Kastler, M.; Pisula, W.; Hofer, W.A.; Fogel, Y.; Wang, Z.H.; Mullen, K.J.Am.Chem.Soc.2006,128,1334.), although this route single step productive rate higher (65%), raw material prepare difficult, do not possess productive value.

At present, pyrene-4,5,9, three synthetic routes of having reported of 10-tetraketone are as follows:

Summary of the invention

The object of the invention is to overcome the defect that prior art exists, provide a kind of new synthetic route to synthesize pyrene-4,5,9,10-tetraketone.

Purpose of the present invention is achieved through the following technical solutions:

A kind of synthetic pyrene-4,5,9, the method for 10-tetraketone comprises the following steps:

(1) adopt 2,6-dioctyl phthalate methyl esters-1-bromobenzene and copper powder to carry out linked reaction in the organic solvent DMF, synthesize 2,2 ', 6,6 '-tetracarboxylic acid methyl esters biphenyl; Raw material 2,6-dioctyl phthalate methyl esters can adopt the method for bibliographical information synthetic ((a) Dahl, B.J.; Branchaud, B.P.Org.Lett.2006,8,5841. (b) Courchay, F.C.; Sworen, J.C.; Ghiviriga, I.; Abboud, K.A.; Wagener, K.B.; Organometallics 2006,25,6074. (c) Ye, L.; Ding, D.Z.; Feng, Y.Q.; Xie, D.S.; Wu, P.H.; Guo, H.; Meng, Q.Q.; Zhou, H.C.Tetrahedron 2009,65, and 8738.).

(2) under nitrogen atmosphere, by 2,2 ', 6,6 '-tetracarboxylic acid methyl esters biphenyl and sodium Metal 99.5 were reflux in toluene 2～4 hours, cooling, after removing the sodium piece, used toluene wash, and organic phase is merged, and added ethanol to guarantee that sodium Metal 99.5 is exhausted; Acid adding is carried out acidification again, after filtering washing, adds salicil amine ethyl cobalt and methyl alcohol, under oxygen atmosphere, reacts, and obtains pyrene-4,5,9, the 10-tetraketone.

Preferably, step 1) linked reaction temperature described in is 120～130 degree, reacts 5～7 hours.

Preferably, acid step 2) is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.

Preferably, step 2) the first reflux of sodium Metal 99.5 and toluene described in, under vigorous stirring, sodium becomes sodium sand, then will be dissolved in 2 in toluene, and 2 ', 6,6 '-tetracarboxylic acid methyl esters biphenyl splashes in sodium sand, then refluxes 2～4 hours.

Step 2) described under oxygen atmosphere reaction conditions be stirred overnight at room temperature, preferred temperature 20 degree, 12 hours time, 200 rev/mins of stirring velocitys.

The present invention synthesizes pyrene-4,5,9, and the variation route of 10-tetraketone is as follows:

With existing pyrene-4,5,9, the synthetic route of 10-tetraketone is compared, and the present invention has the following advantages:

(1) synthetic raw material sources are extensive, and the reagent of employing is all relatively inexpensive reagent as sodium Metal 99.5, copper powder, salicil amine ethyl cobalt etc.

(2) synthesis technique is reliable, mild condition.The Ullmann reaction promoted such as copper powder is classical linked reaction, and the acyloin condensation that sodium Metal 99.5 promotes reaction is also classical reduction reaction, and the oxidizing reaction of salicil amine ethyl cobalt catalysis is also efficient oxidizing reaction.

(3) transformation efficiency of these reactions is all very high, and product is easy to purify.Synthesize 2,2 ', 6, the productive rate of 6 '-tetracarboxylic acid methyl esters biphenyl reaches 78%, synthetic pyrene-4,5,9, and the productive rate of 10-tetraketone reaches 68%.

The accompanying drawing explanation

Fig. 1 is 2,2 ', 6, and the nucleus magnetic hydrogen spectrum of 6 '-tetracarboxylic acid methyl esters biphenyl;

Fig. 2 is 2,2 ', 6, and the nuclear-magnetism carbon spectrum of 6 '-tetracarboxylic acid methyl esters biphenyl;

Fig. 3 is pyrene-4,5,9, the nucleus magnetic hydrogen spectrum of 10-tetraketone.

Embodiment

Embodiment 1

A kind of synthetic pyrene-4,5,9, the method for 10-tetraketone is divided into two steps:

(1) 2,2 ', 6, the preparation of 6 '-tetracarboxylic acid methyl esters biphenyl

103 grams 2,6-dioctyl phthalate methyl esters-1-bromobenzene (purchased from aldrich company), 55 gram copper powders, 180 milliliters of DMFs (DMF) were 125 degree reaction 6 hours, cooling, added 1000 milliliters of toluene, filtered out copper powder.Filtrate is with a large amount of water washings.Add anhydrous magnesium sulfate drying.Filter, revolve except toluene.Obtain brown solid.With 1000 milliliters of ethyl alcohol recrystallizations, obtain 87 gram white powders, productive rate 78%.Fusing point: 128-130 ℃. ¹h NMR (400MHz, CDCl ₃, ppm): 8.144 (d, J=8,4H), 7.503 (t, J=8,2H), 3.558 (s, 12H). ¹³c NMR (100MHz, CDCl ₃): 166.531,142.319,133.176,130.676,127.131,52.042.

(2) pyrene-4,5,9, the preparation of 10-tetraketone

Under nitrogen atmosphere, by 1.2 gram sodium Metal 99.5s and 20 milliliters of toluene reflux, under vigorous stirring, sodium becomes sodium sand, and by 1.16 grams 2,2 ', 6,6 '-tetracarboxylic acid methyl esters biphenyl is dissolved in 10 milliliters of toluene, from the constant voltage separating funnel, splashes in reaction flask.Drip off rear continuation and reflux 3 hours, cooling, the sodium piece solidified is taken out, use toluene wash, organic phase is merged, add ethanol (on a small quantity) to guarantee that sodium Metal 99.5 is exhausted.Then the hydrochloric acid that adds 20 milliliters of 2M, will separate out brown solid in solution, filter, and washing leaching cake is standby.Filter cake and 0.03 gram salicil amine ethyl cobalt, 80 ml methanol are mixed, pass into oxygen, stirred overnight at room temperature, solution will become orange, filter after washing, drying.Cross post with silica gel, methylene dichloride is elutriant, finally uses ethyl alcohol recrystallization, obtains 0.54 gram pyrene-4,5,9, and the 10-tetraketone is orange powder shape solid, productive rate 68%. ¹h NMR (400MHz, DMSO, ppm): 8.300 (d, J=8,4H), 7.709 (t, J=8,4H). ¹³cNMR (solubleness is too low, fails to measure).

Claims

1. synthetic pyrene-4,5,9, the method for 10-tetraketone, is characterized in that, comprises the following steps:

(1) adopt 2,6-dioctyl phthalate methyl esters-1-bromobenzene and copper powder to carry out linked reaction in the organic solvent DMF, temperature of reaction is 120～130 degree, reacts 5～7 hours; Synthesize 2,2 ', 6,6 '-tetracarboxylic acid methyl esters biphenyl;

(2) under nitrogen atmosphere, by 2,2 ', 6,6 '-tetracarboxylic acid methyl esters biphenyl and sodium Metal 99.5 were reflux in toluene 2～4 hours, cooling, after removing the sodium piece, used toluene wash, and organic phase is merged, and added ethanol to guarantee that sodium Metal 99.5 is exhausted; Acid adding is carried out acidification again, after filtering washing, adds salicil amine ethyl cobalt and methyl alcohol, under oxygen atmosphere, reacts, and the temperature of reaction is 20 degree, and the time is 12 hours, 200 rev/mins of stirring velocitys; Obtain pyrene-4,5,9, the 10-tetraketone.

2. method according to claim 1, is characterized in that step 2) described in acid be one or more in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid.

3. method according to claim 1 and 2, is characterized in that step 2) described in the first reflux of sodium Metal 99.5 and toluene, under vigorous stirring, sodium becomes sodium sand, then will be dissolved in 2 in toluene, 2 ', 6,6 '-tetracarboxylic acid methyl esters biphenyl splashes in sodium sand, then refluxes 2～4 hours.