WO2010118660A1

WO2010118660A1 - Method for synthesizing substituted anthraquinone with high purity

Info

Publication number: WO2010118660A1
Application number: PCT/CN2010/071403
Authority: WO
Inventors: 戴雷; 蔡丽菲; 赵洪玉; 邵立柏
Original assignee: 北京阿格蕾雅科技发展有限公司
Priority date: 2009-04-13
Filing date: 2010-03-30
Publication date: 2010-10-21
Also published as: CN101514153B; CN101514153A

Abstract

Disclosed is a method for synthesizing substituted anthraquinone with high purity. The substituted anthraquinone is obtained by the following step: the product which is obtained by reacting 3-X₁ substituted benzoic acid anhydride with X₂ substituted benzene is dehydrated in the presence of dehydrant. The process of the present invention optimizes the reaction route and avoides the side reactions; thereby the method can be used in the industry production. The product obtained by the process of the present invention is soluble and its color is white; therebythe product can be used to produce organic luminous materials and field effect transistors.

Description

Synthesis method of high purity substituted hydrazine

The invention belongs to the technical field of intermediate preparation of synthetic organic light-emitting materials and field effect transistor materials, in particular to a synthesis method of high-purity 2-substituted and 2,6-disubstituted anthracene.

Background technique

Anthracene derivatives are important raw materials for bismuth series of compound dyes, organic dyes and other chemical products, of which β-蒽醌 is the most valuable. With the development of OLEDs and field-effect transistors in various countries, the demand for terpenoids has also increased (Seung Kyu Lee et al., organic letters, 05, 7: 323-326, Wang Xinhua et al., organic letters, 08, 10 : 641- 644, J. -Η· Park et al., organic letters, 07, 9: 2573- 2576). There are many synthetic methods for hydrazine: direct oxidation, displacement, Firedel-Crafts, etc. The hydrazine derivatives obtained by these synthetic methods can be used in the dye industry, but it is difficult to meet the requirements as an electronic product, and the purity is not high. , difficult to purify and other issues. In the organic semiconductor industry, ruthenium is widely used as a blue light material and a field effect transistor material (LG Chem. CN1898355, Kodak US7326371, EP1156536, Wang Fosong et al., organic letters, 06, 8: 785-788); Mainly 2-substituted and 2,6-disubstituted) Various groups can be introduced to obtain cerium materials with different properties. These materials are used in light-emitting devices to improve device lifetime and reduce startup voltage. Therefore, scientists from all over the world Put a lot of effort into research and development in the field of terpene materials. Beta-substituted anthracene derivatives (mainly 2-substituted and 2,6-disubstituted) are intermediates in the synthesis of these anthracene derivatives (masahiro kamamura, US20070200490, Kaname Ito et al., Angew. Chem. Int. Ed., 2003, 42, No. 10: 1159-1162, J.-H. Park et al., organic letters, 07, 9 : 2573-2576 ), so the development of β-substituted anthracene derivatives is significant; because trace impurities seriously affect the device The performance, so the key is to develop high purity beta substituted anthracene derivatives. The β-substituted indole synthesis method reported in the literature mainly focuses on group transformation, such as the synthetic methods mentioned in World Patent No. W002053545 W003095445, Seung Kyu Lee et al., Organic Letters, 05, 7: 323-326, which are dyes. Industrial products are raw materials, and the synthesized compounds do not mention the characterization of purity; more importantly, the quinone compounds are very active in the aromatic ring, and there are many side reactions, which are difficult to purify by common purification methods. There are also reports in the literature, such as Applied Chemistry, 2006, 23 (7), 812 The method can only be used in the laboratory, it is difficult to industrialize; Lin et al. proposed the method of treating 2-methyl hydrazine by Firedel-Crafts method (dye and dyeing, 04, 41: 289-283), but at the end of the ring A large amount of low-boiling organic solvent is used, and the solvent is distilled off during the reaction, which is difficult to control in the industrial process.

The inventors of the present invention summarized the current synthetic β-substituted hydrazine literature and found that: the current method has certain defects, on the one hand, the raw material is impure, on the other hand, the synthesis process is prone to side reactions, and the by-products produced are difficult to purify, resulting in synthesis. Photoelectric materials cannot be used. Beta-substituted ruthenium is an intermediate in the synthesis of organic luminescent materials and field effect transistor materials. The synthesis of high purity ruthenium is the key to the development of these materials. In order to obtain an anthracene derivative used in an electronic material, it is necessary to find a good synthesis method and to achieve industrialization.

Summary of the invention

The invention finds a rapid, efficient and simple synthetic route, and the obtained intermediate and the final product can be directly used without cumbersome purification.

a method for synthesizing compound I,

(I)

Wherein Χ _{1 =} oxime, halogen, d- ₄ alkyl, X ₂ = halogen, d- ₄ alkyl.

The method comprises the following steps: (1) Substituting phthalic anhydride with X ₂ -substituted benzene under the catalysis of anhydrous aluminum trichloride to form a compound II, (2) Compound II loses a molecule of water ring under the action of a shrinking agent Compound I was obtained.

The step (2) shrinking agent is concentrated sulfuric acid, concentrated phosphoric acid, concentrated hydrochloric acid or acetic acid, and the reaction temperature is 100-200.

°C.

It is preferably 100-160 °C.

In the step (2), the compound II is added to the water-reducing agent in portions, and then heated to 100 to 20 CTC for 4 to 5 hours.

The end point of the step (2) reaction is indicated as obtaining a uniform reaction solution.

The compound II used in the step (2) is obtained by pouring the reaction product of the step (1) into a solid precipitated in ice water, and drying by filtration. In the step (1), the amount of aluminum trichloride is 2-3 times the molar amount of the substituted phthalic anhydride, and the reaction temperature is 30-100 °C.

It is preferably 40-70 °C.

Wherein X _{1 =} H, X ₂ = Br or X _{1 =} Br, X ₂ = Br, I, Cl, methyl, ethyl, tert-butyl, isopropyl.

The invention uses phthalic anhydride and derivatives, bromobenzene (chlorobenzene, toluene, ethylbenzene, propylbenzene) industrial raw materials as raw materials, and is cheap, easy to obtain, and does not require special purification. Aluminum trichloride is added in portions and reacted at a certain temperature to obtain a solution to stop the reaction without detecting and tracking. This is a typical gram-gram addition reaction. The reaction solution is poured into a certain amount of ice-water to obtain white solid II. There is no tar and incomplete phenomenon. After separation and drying, it can be directly put into the next step. The product is separated by a very method, and the product can be directly used in the next step without further purification. The reaction is more conducive to industrial production. Under the action of the shrinking agent, the white solid II only needs to be raised to a certain temperature to react. A uniform solution is obtained to prove the end of the reaction, and then poured into ice-water to obtain more than 99% of the white product, without purification and decolorization, and no carbonization. Phenomenon, the product is easily soluble in common organic solvents such as THF and CHC1 ₃ . It is completely different from the general Firedel-Cmfts requiring low temperature reaction. We are based on the literature (masahiro kamamura, US20070200490, Kaname Ito ^Λ» Angew. Chem. Int. Ed., 2003, 42, No. 10: 1159-1162, J. - H. Park et al., organic letters, 07, 9 The method of 2573-2576) was carried out in a comparative manner. 2-Aminoguanidine and 2,6-diaminopurine were reacted with copper bromide and t-butyl nitrite to obtain a multi-substituted product. A pure compound cannot be obtained by repeated recrystallization, silica gel column or the like, and the product has little solubility in a solvent such as THF, which is disadvantageous for further reaction. The product obtained by the method of the present invention is relatively soluble and the color is white, which facilitates the synthesis of the organic light-emitting material and the field effect transistor material.

On the basis of reading a large amount of literature, the inventors proposed the route of the present invention, optimized the literature route, avoided the generation of side reactions, and facilitated industrialization.

Compared with the literature reporting method, the present invention has the following advantages:

1. Synthetic is efficient, fast, environmentally friendly and easy to industrialize.

2. There are no by-products in the synthesis process to avoid cumbersome purification.

3. In addition to the compounds referred to in the present invention, the method can be analogized to analogous compounds and has a wide range of uses. 4. The product I obtained by the method of the invention has good solubility and can participate in the reaction at low temperature, and is used as an intermediate material of the organic light-emitting material and the field effect transistor material.

DRAWINGS

Fig. 1 is a nuclear magnetic diagram of Embodiment 1.

Fig. 2 is a nuclear magnetic diagram of Embodiment 2.

Figure 3 is a nuclear magnetic diagram of Embodiment 3.

Figure 4 is a nuclear magnetic diagram of Embodiment 4.

Figure 5 is a nuclear magnetic diagram of Embodiment 5.

Figure 6 is a nuclear magnetic diagram of Embodiment 7.

Figure 7 is a nuclear magnetic diagram of Embodiment 8.

detailed description

A better understanding of the present invention can be obtained by the following description of the preferred embodiments and the accompanying drawings.

Example 1

2-Bromoguanidine synthesis route:

1-1:

785G bromobenzene and 148G phthalic anhydride were added to a 500 ML four-necked flask, and aluminum 355G was added in portions at room temperature, and the solution turned pale yellow. Raise the temperature, react at 50-60 ° C for 5 hours to obtain a homogeneous solution; pour into ice, filter, wash the solid with 200 ML of water to obtain a white product, and dry at 70 ° to obtain 250G, yield 80%.

^{HNMR (400MHz, d 6 -DMSO,} TMS) δ (ppm): 7.96 (d, lH), 7.67 (m, 3H), 7.61 (m, lH), 7.50 (d, 2H), 7.34 (d, lH) o See Figure 1

1-2:

Add 1000G concentrated sulfuric acid, the first step product 209G is added in reddish brown, increase the temperature to 150 160 ° C, the color turns reddish brown, react for 4 hours, pour into 500ML water and 500G ice, precipitate a large amount of white solid, stir filter. It was washed twice with 400 ml of water, washed with 200 ML of ethanol; dried to obtain 157 g, yield 80%.

HNMR (400MHz, CDCl ₃ , TMS) δ (ppm): 8.44 (s, lH), 8.32 (s, 2H), 8.17 (d, lH), 7.94 (d, lH), 7.84 (d, 2H) o See figure 2. The nuclear magnetic detection is very pure and can meet the comparative requirements of electronic materials:

90 g of 2-aminopurine (95%), 108 g of copper bromide, and acetonitrile 1 L were added to a 2 L four-necked flask and stirred with nitrogen for 30 minutes. The temperature was raised by 65 °C, and t-butyl nitrite was added dropwise. After 2 hours of dropwise addition, a large amount of solid yellow solid was produced, and no raw material was present on the plate. The reaction was stopped and treated with dilute hydrochloric acid. The methanol was purified 3 times and subjected to column treatment to obtain 61.5 g, yield 66%, and there were still many impurities in the nuclear magnetic detection. See Figure 3 Example 2

2, 6 dibromofluorene synthesis route:

2-1: Synthesis of 4-bromophthalic acid

101G sodium hydroxide, 800ML water was added, 176G phthalic anhydride was added in portions, and the solution was completely dissolved. Bromine 64ML was added dropwise, and the reaction was increased by 90 degrees for 6 hours. Filtered, the solid was stirred with 400 ML of water. Filtration gave a white solid. A 2 L four-necked flask was added, and 1000 ml of water was completely dissolved by heating, and the precipitated solid was cooled to 134.8 G, and the yield was 45.7%.

H NMR (400 MHz, acetone, TMS) δ ( _ppm ): 8.16 (s, lH), 8.03 (d, 2H), 7.89 (d, lH). See the figure

2-2: Synthesis of 4-monobromophthalic anhydride

The 90G raw material and 300 ML of acetic anhydride were added to a 1 L four-necked flask, heated under reflux for 4 hours, and then the solvent was substantially free of liquid. A large amount of solid was precipitated by cooling, 150 ml of petroleum ether was stirred, filtered, and washed twice with 200 mL of petroleum ether, 73.6 g, yield 88%.

H NMR (400 MHz, CDC1 ₃ , TMS) δ (ppm): 8.16 (s, lH), 8.03 (d, 2H), 7.89 (d, lH). see

2-3:

176 bromobenzene, the first step product 47G was added to a 500ML four-necked bottle, and aluminum trichloride 75G was added in batches, and the reaction liquid turned reddish brown. Raise the temperature 50-60 degrees, the reaction liquid turns light brown, react for 5 hours, pour into 150ML ice-water; wash the solid with dilute hydrochloric acid solution to obtain white product suction filtration, and obtain 70 degree drying, 73.4G, Yield 85%

2-4:

Add 240G concentrated sulfuric acid, the third step product 47.4G is added in reddish brown, the temperature is increased to 150-160 degrees, the color turns reddish brown, the reaction is 4 hours, poured into 100ML water, a large amount of solid is precipitated, and stirred and filtered. Wash twice with 400 ML water, 200 ML ethanol; dry to give 41G, 90% (HPLC 99.4%) o

H NMR (400 MHz, CDC1 ₃ , TMS) δ (ppm): 8.44 (s,lH), 8.2 (d,lH), 7.9 (d,lH). See the figure

Comparative example 2:

70 g of 2,6-diaminopurine (95%), 160 g of copper bromide and acetonitrile 800 ml were added to a 2 L four-necked flask and stirred under nitrogen for 30 minutes. The temperature was raised by 65 °C, and t-butyl nitrite was added dropwise. After 2 hours of dropwise addition, a large amount of earthy yellow solid was produced. No material was present on the plate, the reaction was stopped, and treated with 20% dilute hydrochloric acid. The ethanol was washed twice, and the 1, 4-dioxane was purified 4 times, and the column was treated to obtain impurities (tetrabromofluorene) in the nuclear magnetic detection of the product.

HNMR (400MHz, CDC1 ₃ , TMS) δ (ppm): 8.44(s,lH), 8.2(d,lH), 7.9(d,lH), 8.5 (tetrabromofluorene). See Figure 7. Example 3:

The concentrated sulfuric acid in Example 1 was changed to concentrated phosphoric acid, and the results were the same, which was easier to handle.

Example 4:

The concentrated sulfuric acid in Example 1 was changed to acetic acid, and the results were the same.

Example 5

The concentrated sulfuric acid in Example 2 was changed to concentrated phosphoric acid, concentrated hydrochloric acid, and acetic acid, and the results were the same.

Example 6:

2-bromo-6-chloropurine:

Using the same method, 2-bromo MS (FD) can be synthesized using the starting material 4-monobromophthalic anhydride or chlorobenzene: 317. 6

Example 7

2-bromo-6-methyl hydrazine:

In the same manner, 2-bromoindole can be synthesized using the starting material 4-bromophthalic anhydride or toluene. MS (FD): 297. 189

Claims

Claim

1. Synthesis method of compound I,

(I)

Wherein X _{1 =} H, halogen or d- ₄ alkyl, X ₂ = halogen or d- ₄ alkyl.

The method comprises the following steps: (1) 3-substituted phthalic anhydride and X ₂ substituted benzene undergoing a gram-gram reaction under the catalysis of anhydrous aluminum trichloride to obtain compound II, (2) compound II loses one molecule of water under the action of a shrinking agent Compound I is obtained by ring closure.

The synthesis method according to claim 1, wherein the step (2) is a concentrated sulfuric acid, concentrated phosphoric acid, concentrated hydrochloric acid or acetic acid, and the reaction temperature is 100-200 °C.

3. The method of synthesis according to claim 2, wherein the reaction temperature is 100-16 CTC.

The synthesis method according to claim 2, wherein the step (2) is: adding the compound II to the water-reducing agent in portions, and further heating to 100 to 20 CTC for 4 to 5 hours.

The synthesis method according to claim 1, wherein the end point of the reaction of the step (2) is indicated to obtain a uniform reaction solution.

The synthesis method according to claim 1, wherein the compound II used in the step (2) is obtained by pouring the reaction product of the step (1) into a solid precipitated in ice water and drying by filtration.

7. The method according to claim 1, wherein in the step (1), the amount of aluminum trichloride is 2-3 times the molar amount of the 3-X substituted phthalic anhydride, and the reaction temperature is 30-10 CTC.

8. The method according to claim 7, wherein the reaction temperature is 40 to 70 °C.

The synthesis method according to any one of claims 1 to 8, wherein, Χ^Η, Χ^Βι·, or Χ _{1 =} Br, X ₂ = Br, I, Cl, methyl, ethyl, tert-butyl Base or isopropyl.