JPS58124789A - Anthraquinonetetracarboxylic acid dianhydride derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI(W, X, Y and Z are H, fluoro, chloro, bromo, iodo, OH, <=8C alkoxyl, acetoxyl or cyano). EXAMPLE:1, 4, 5, 8-Tetramethoxy-2, 3: 6, 7-anthraquinonetetracarboxylic acid dianhydride. USE:A raw material for preparing high polymeric condensed polycyclic compounds, e.g. a raw material for preparing novel compounds of formula II useful as a high polymeric electronic material, acting as an electron acceptor, and having the property of forming a charge transfer complex with a suitable electron donor. PROCESS:A compound of formula III and a compound of formula IV are reacted with H2SO4 according to the reaction formulas to give a compound of formula V, which is then treated with potassium permanganate and acetic anhydride one after another to afford the aimed compound, e.g. a compound of formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds, 2,3:6°7-anthraquinonetetracarboxylic dianhydride derivatives.

Anthraquinone and its various derivatives have been produced and widely used industrially as dyes or raw materials thereof. However, there have been few examples of these compounds being used as raw materials for producing industrially useful polymeric compounds, particularly fused polycyclic polymeric compounds in which a large number of benzene rings are condensed.

Under these circumstances, the present invention provides a novel compound that takes advantage of the characteristics of anthracene derivatives that are used as raw materials for producing industrially useful polymer compounds, particularly polymer fused polycyclic compounds. be.

The novel compound of the present invention is represented by the structural formula 2
, 3:6,7-anthraquinonetetracarboxylic dianhydride derivative (hereinafter referred to as the derivative of the present invention). In the first formula, W, X, Y and Z are a hydrogen group, a fluoro group, and a chloro group, respectively.

It is assumed that the group is one arbitrarily selected from the group consisting of a bromo group, an iodo group, a hydroxyl group, an alkoxy group having 8 or less carbon atoms, an acetoxy group, and a cyan group.

In addition, in this specification, the symbols w, x, y, and 2 are defined as any one of the substituent groups listed above.

(1) The derivative of the present invention can be reacted with, for example, an aromatic compound that is susceptible to electrophilic reactions to derive a high molecular weight polycarboxylic acid or a salt thereof. Furthermore, by subjecting these polycarboxylic acids to intramolecular dehydration condensation, a polymer compound having a ring structure having a carbonyl group can be obtained. Among these aromatic compounds, if you select a compound that has a ladder-shaped carbon skeleton and has hydrogen atoms only at the four carbon atoms at both ends, it will be a particularly novel and useful ladder-shaped polymer. A fused polycyclic compound is obtained. It is used for such aromatic compounds and polymer beams. Here, the aromatic compound refers to a benzene ring or a compound containing a condensed benzene ring. .

OHOH0H OI(OH0H (2) (3) The various types of polymer compounds mentioned above are industrially useful compounds that can be applied to a wide range of applications, and the derivatives of the present invention are important as raw materials for them. .The configuration of the present invention will be explained in detail below.

The derivative of the present invention has the following molecular structural and chemical characteristics.

1) Molecular structural characteristics The anthracene skeleton and the carbon atoms of the anhydrated carboxyl group of the derivative of the present invention have a ladder skeleton.

It can be seen in the fourth formula that the pair of chains consisting of these carbon atoms are symmetrical with respect to the axis of symmetry S.

The main feature of the present invention is that it has a long ladder skeleton consisting of 18 carbon atoms.

(4) 2) Chemical characteristics The derivatives of the present invention have high reaction activity in dehydration condensation reactions with aromatic compounds. For this reason, a polymer compound using a dehydration condensation reaction can be easily obtained. This can be explained by the sensitivity effect and resonance effect, which are well known in organic synthetic chemistry. That is, the derivative of the present invention has an oxygen atom directly bonded to the anthracene skeleton, and the electron density of the anthracene skeleton decreases due to the electron-withdrawing property of this oxygen atom. This results in 2.3
．． The electrons existing on the bond between the carbon atoms at the 6 and 7 positions and the carbon atom of the carbonyl group are attracted toward the anthracene skeleton, and a proton or a When the ether bond is cleaved by attack by a reagent such as a Lewis acid, the carbon atom on the carbonyl group becomes positively charged and is strongly polarized by δ+ from the anthracene skeleton.

Therefore, this positively charged carbon atom can be interpreted as having a strong electrophilic aggressiveness toward aromatic compounds.

This tendency is further promoted when a highly electron-withdrawing substituent such as a fluoro group or a cyan group is bonded to either the 1st, 4th, 5th or 8th carbon atom, and the reactivity is further increased.

(6) Due to these molecular structural and chemical characteristics, industrially useful polymer compounds, especially polymer fused polycyclic compounds, can be easily obtained.

Next, the effects of the present invention will be described, and the present invention and a conventional example will be compared.

One of the main effects of the present invention is that a ladder type polymer condensed polycyclic compound as shown in Formula 3 can be obtained by reaction with an aromatic compound as shown in Formula 2. This is due to the symmetry of the molecular structure shown in the fourth formula. In addition, as will be described later, it is easy to obtain a highly pure 2D-1 type polymer condensed polycyclic hydrocarbon compound in which pentacene or a larger number of benzene rings than pentacene have been condensed, for which high-purity products have not been obtained in the past. This is also a major effect of the present invention.

3) Polymer condensed polycyclic compounds Using the derivatives of the present invention, various ladder-type polymer condensed polycyclic compounds having a wide range of molecular weights from relatively low to high molecular weights can be easily obtained.

3.1) Boriacene derivative The derivative of the present invention and, for example, 1°4.6,
A polyacene derivative represented by formula 3 is obtained by reaction with 8,9,10-hexahydroxyanthracene.

3.2) Polymer condensed polycyclic hydrocarbon compounds Polymer condensed polycyclic hydrocarbon compounds are important as raw materials for producing various polymer condensed polycyclic compounds.

For example, highly pure heptacene can be easily produced by the reaction of formula 6. A similar reaction yields a ladder type polymer condensed polycyclic hydrocarbon compound in which many more benzene rings are condensed.

Below Margin Br Br Br Particularly, in the past, it was difficult to obtain high-purity ladder-type polymer condensed polycyclic hydrocarbon compounds such as hebutacene in which several or more benzene rings are condensed, but with the action of the present invention, it is easy to obtain. become. As mentioned in the section of molecular structural characteristics in 2), this effect can be achieved if the molecule of the derivative of the present invention has a long ladder skeleton, and if appropriate substituents are selected for w, x, y, and 2, e.g. This results from the fact that reactivity, solubility, etc. can be adjusted appropriately. Furthermore, a condensed polycyclic hydrocarbon compound with a higher molecular weight can be obtained from the polyacene derivative described in 3.1) by a reaction similar to that of the sixth formula.

Next, the effects of the present invention will be described. It is thought that the derivative of the present invention is based on a decrease in the electron density on the anthracene skeleton due to the electron-withdrawing property of the oxygen bonded to the 10-position and the anhydrous carboxyl group. This property is even more remarkable in compounds having a highly electron-withdrawing substituent such as a fluoro group or a cyan group on at least one of the 1st, 4th, or 8th carbon atoms.

4) Comparison with conventional examples In the past, attempts have been made to synthesize ladder-type polymer condensed polycyclic hydrocarbon compounds in which several or more benzene rings are condensed. For example, 'w'V, T, Ba1
lay at ale, J, Am, Chem,
Soc, 20°5603 (1953), has 1,2-
A method for preparing pentacene from dimethylene t-hexane and P-benzoquinone is described. Also, 2,3-
A method for producing pentacene using dimethylene decalin and P-benzoquinone is described in Kagaku Daijiten Editorial Committee Cotton, Daigakuinu Dictionary, Vol. 8, p. 368, Kyoritsu Shuppansha (1962). However, these methods generally yield only crudely crystalline compounds, and the yields are also quite low. Furthermore, these compounds have high reactivity and extremely low solubility and sublimation, making purification extremely difficult and making it extremely difficult to obtain highly pure crystals.

For similar reasons, it is still difficult to obtain highly pure ladder-type polymer-fused polycyclic hydrocarbon compounds in which many more benzene rings are fused, and it is difficult to obtain accurate physical constants such as melting point for compounds with molecular weights greater than heptacene. It has not been done.

In addition, as compounds similar to the polyacene derivatives listed in 3.1), for example, H, A, Pohl at al.
,.

J, Phys, Chem, 66, 2085 (1
962): 1 bid.

66.2121 (1962), etc., polyacenequinone radical (PAQR) is listed. These compounds have been widely studied as interesting semiconductor materials.

However, the production of these compounds requires rather strong reaction conditions; for example, in the literature of Pohl et al., high temperature conditions of about 250-300° C. are selected.

This requires consumption of a large amount of power, energy, etc.

Comparing these results, it can be seen that by using the derivatives of the present invention, various useful polymer compounds, including ladder-type polymer-fused polycyclic hydrocarbon compounds, can be easily obtained, indicating that the derivatives of the present invention have excellent properties.

Next, an outline of the method for producing the derivative of the present invention will be described.

A typical example is 1,4,5,8-tetrachloro-23:6
．． The scheme of the method for producing 7-anthraquinonetetracarboxylic dianhydride is shown in Formula 7. Other compounds of the invention can be prepared by much the same route.

The present invention will be explained in further detail by giving examples below.

Below Margin OCfi OCR CQ O(4 ci ocx OCQ OCQ Q Example 1 1.4,5.'8-tetramethoxy2,3:6゜Production of 7-anthraquinonetetracarboxylic dianhydride3. 6-Simethoxy 1.2: 0.3 mol of 4,6-benzenetetracarboxylic dianhydride and 0.1 mol of 3,6-simethoxy-xylene were added to 500 tug of concentrated sulfuric acid and heated to 120°C. After cooling the solution, it was poured into a large amount of cold water to precipitate crystals.This was thoroughly washed with cold water and dried to obtain crystals of 40.8y.

This crystal 35, f5jF was collected and dissolved in dimethyl sulfoxide 6oorILl, and potassium permanganate was suspended in the solution and heated to 160°C.
Stir for hours. After this solution was cooled, it was poured into a large amount of cold water to precipitate crystals, and recrystallized from methyl isobutyl ketone. crystals were obtained.

The thus obtained crystals were separated at 25.2F, heated in acetic anhydride, cooled, and filtered to obtain a lumpy solid. This was thoroughly stirred in ether, washed, filtered, and further recrystallized from methyl isobutyl ketone to obtain crystals of 16.91.

A reaction similar to the reaction leading to the acid anhydride used here is described, for example, by B, H, N1colet et al., Org.
.

5ynth, I, 410 (1941).

From the results of elemental analysis of the crystal thus obtained, this compound has a compositional formula of C11H606, and analysis by infrared absorption spectroscopy revealed deep absorption near 180 ocrn, which is believed to be due to anhydrous carboxyl groups. Also,
Results of proton NMR spectrum analysis, 4. Op
It was found that a sharp absorption peak was observed near pm. From these analysis results, the obtained compounds are 1.4, 5, 8,
It was identified as 9,10-tetramethoxy-2,3:6,7-anthraquinone tetracarboxylic dianhydride.

Example 2 1.4,5.8-tetrahydroxy-2,3:6.7-
Preparation of anthraquinonetetracarboxylic dianhydride 3-hydroxy-6-chloro-1,2:0.3 mol of 4,5-benzenetetracarboxylic dianhydride and 0.3 mol of 3-hydroxy-6-chloro-0-xylene. 1 mol and 60f of boric acid were dissolved in 60oIILl of concentrated sulfuric acid and heated at 200°C.
and stirred for 4 hours. Thereafter, the reaction solution was poured into cold water, and the precipitated crystals were separated by filtration and then boiled in boiling water, followed by hot filtration and washing with hot water.

The crystals thus obtained were treated sequentially with potassium permanganate and acetic anhydride in the same manner as in Example 1,
A crystal of 18.5F was obtained.

As a result of elemental analysis of the crystal thus obtained, this compound has a compositional formula of C9H206, and analysis by infrared absorption spectroscopy shows that there is a deep absorption near 1800 cm −' that is thought to be due to anhydrous carboxyl group, and that the compound has a composition formula of C9H206.
A slightly broad absorption peak was obtained near crn, which was thought to be due to hydroxyl groups. The compound obtained from these analysis results is 1.4,5.8-tetrahydroxy-2,3:6,
It was identified as 7-anthraquinone tetracarboxylic dianhydride.

In addition, 3-hydroxy-6-chloro-1,2:4.6-
Benzene tetracarboxylic dianhydride was obtained by hydrolyzing P-dichlorobenzene to obtain a monohydroxy substituted product, which was then tetramethylated and then oxidized and dehydrated.

Example 3 1.4,6.8-tetraacetoxy-2,3:6.7-
Production of anthraquinone tetracarboxylic dianhydride 1,4,5.8-tetrahydroxy-2,3;6,7-anthraquinone tetracarboxylic dianhydride obtained in Example 2 was mixed with acetic anhydride and concentrated sulfuric acid. The mixture was poured into the solution and stirred while heating.

Thereafter, the reaction solution was cooled to precipitate crystals, which were further stirred in acetic anhydride while heating.

The solid mass obtained upon cooling was treated in the same manner as in the final reaction step of Example 1 to obtain crystals. The crystals were dissolved in tetrahydrofuran, and a solution was separated into each fraction by GPC method. Among these, a crystal was extracted from the fraction corresponding to the main peak, and as a result of elemental analysis, this compound had a composition formula of C13H608, and as a result of proton NMR spectrum analysis, it was found to be 2.6pp.
A sharp absorption peak was obtained near m. From these analysis results, the obtained compound was identified as 1.4,5.8-tetraacetoxy-2,3:6,7-anthraquinonetetracarboxylic dianhydride.

Example 4 Production of 1.4,5.8-tetrachloro-2,3:6゜7-anthraquinonetetracarboxylic dianhydride 3.6-dichloro-1,2:4,5-benzenetetracarboxylic dianhydride 0.3 mol of anhydride and 3,6-dichloro-〇-
0.1 mol of xylene (D) was dissolved in concentrated sulfuric acid, heated to 120°C and stirred for 4 hours. After cooling this solution, it was poured into a large amount of cold water to precipitate crystals, which Wash thoroughly with cold water.

The thus obtained crystals were sequentially treated with potassium permanganate and acetic anhydride in the same manner as in Example 1 to obtain crystals of 20.43*.

As a result of elemental analysis, this compound was C9o4CI!
, 2, and showed deep absorption near 180oσ-1 when analyzed by infrared absorption spectroscopy.

From these analysis results, the obtained compound has a molecular weight of 1.4°6.
It was identified as 8-tetrachloro-2,3:6,7-anthraquinonetetracarboxylic dianhydride.

Example 6 1,4,5,8-tetrafluoro-2,3; Production of 6゜7-anthraquinonetetracarboxylic dianhydride 1,4,5,8-tetrachloro-2 obtained in Example 4 , 3: 0.3 mol of 6,7-anthraquinonetetracarboxylic dianhydride and 10 oy of potassium fluoride in 5
The mixture was dissolved in dimethyl sulfoxide 7, and stirred under reflux for 4 hours while heating. After the reaction solution was cooled, it was poured into a large amount of dry ice acetone to precipitate crystals. These crystals were further treated in acetic anhydride in the same manner as in Example 1 and recrystallized from dimethyl sulfoxide to obtain a crystalline solution of 11.85! crystals were obtained.

As a result of elemental analysis of the crystal thus obtained, it was found that this compound had a composition formula of 0904F2, and analysis by infrared absorption spectroscopy showed deep absorption near 180 ocrn. From these analysis results, the obtained compound was 1,4,5.8-tetrafluoro-2,3;
It was identified as 6,7-anthraquinone tetracarboxylic dianhydride.

Incidentally, a reaction similar to the fluorination reaction used in this example is described, for example, by Nobuo Ishikawa et al., Organic Synthetic Chemistry, 17.17.
5 (1969).

Example 6 Production of 1.4,5.8-tetracyano-2,3:6゜7-anthraquinonetetracarboxylic dianhydride 3.6-dicyano-1.2;4,5-benzenetetracarboxylic dianhydride 0.3 mol and 3,6-dichloro-0-
0.1 mole of xylene and 6oOWtl! The solution was dissolved in concentrated sulfuric acid, heated to 120° C. and stirred for 4 hours. After cooling, this solution was poured into a large amount of cold water to precipitate crystals, which were thoroughly washed with cold water.

The crystals thus obtained were dissolved in dimethyl sulfoxide, cupric cyanide powder was added thereto, and the mixture was refluxed for 4 hours with stirring. After the reaction solution was cooled, it was poured into a large amount of cold water to precipitate crystals, which were thoroughly washed and treated with potassium permanganate and acetic anhydride sequentially in the same manner as in Example 1. Recrystallization from sulfoxide gave 9.8F crystals.

As a result of elemental analysis of the crystals obtained in this way, this compound was found to be 0
It has a compositional formula of 11N204, and analysis by infrared absorption spectroscopy revealed that it exhibits deep absorption near 18oocIn, which is thought to be caused by anhydrous carboxyl groups, and a sharp absorption near 22oocrn, which is thought to be caused by cyano groups. From these analysis results, the obtained compounds are 1.
It was identified as 4,5,8-tetracyano-2,3:6,7-anthraquinone tetracarboxylic dianhydride.

Incidentally, a reaction similar to the cyanation reaction used in this example is described by, for example, H, O, House et al.

1, Org, Chem,, 34, 3626 (1
969), etc.

In addition, the 3,6-dicyano-1,
2:4,5-Benzenetetracarboxylic dianhydride was obtained by oxidation and dehydration of dicyanodurene obtained by cyanating dichlorodurene. .

Example 7 Various types of 1.4 produced by the same method as Example 1
, 5.8-tetrahydroxy-2,3; A tetraalkyl ether derivative of 6.7-anthraquinone tetracarboxylic dianhydride was prepared.

Table 1 shows examples of the compounds of the present invention, listing the names of the reactants and product substances, and the method for identifying the product substances.

Table 1: Production of various derivatives (1) Notes: 1. Only the compounds used in the first stage reaction are shown in the reactant column.

2 EA, NMR and IR are elemental analysis methods, respectively.
Abbreviation for proton NMR spectroscopy and infrared absorption spectroscopy.

3 In the proton NMR method, numerical values are shown in ppm units. Also, in the symbols in parentheses, 8 is a sharp absorption peak, 2, 3 and 4 are doublet, triplet and quadruplet, respectively.
These precautions also apply in Table 2.

Example 8 Various types of 1.4 prepared by the same method as Example 4
, 6.8-tetrano10geno2,3:6°7-7traquinosochitracarboxylic dianhydride was prepared. Table 2 shows examples of the compounds of the present invention, listing the names of the reactants and products, and the identification method of the product.

Claims (1)

[Claims] A 2,3:6,7-anthraquinonetetracarboxylic dianhydride derivative represented by the general formula below. (However, w, x, y and 2 are each hydrogen groups. Fluoro group, chloro group, bromo group, iodo group, hydroxyl group,
It is assumed that the group is one arbitrarily selected from the group consisting of an alkoxy group having 8 or less carbon atoms, an acetoxy group, and a cyano group. )