CN112939758B - Preparation method of organic optical material - Google Patents

Preparation method of organic optical material Download PDF

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CN112939758B
CN112939758B CN202110172480.XA CN202110172480A CN112939758B CN 112939758 B CN112939758 B CN 112939758B CN 202110172480 A CN202110172480 A CN 202110172480A CN 112939758 B CN112939758 B CN 112939758B
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temperature
adjusting
filtering
anthraquinone
powder
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CN112939758A (en
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王崇年
刘长波
江志强
王越
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Dalian Trico Chemical Co ltd
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Dalian Trico Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a preparation method of an organic optical material, belonging to the technical field of organic chemistry. The method comprises the following steps: preparing 9, 10-dialkoxy (substituted) anthraquinone by adopting a one-pot method; the mixed metal powder used in the method is zinc powder and other metal powder; the other metal powder is iron powder, tin powder, aluminum powder or nickel powder. The preparation method provided by the invention is simple to operate, has low requirements on equipment, has the conversion rate of over 99 percent, the product purity of over 99 percent and the product yield of over 92 percent, and can be applied to industrial production in a large scale so as to meet the ever-increasing market demand.

Description

Preparation method of organic optical material
Technical Field
The invention relates to a preparation method of an organic optical material, belonging to the technical field of organic chemistry.
Background
9, 10-dialkoxy (substituted) anthraquinones are organic optical materials and there are many methods for synthesizing these compounds. The anthraquinone derivative used in the research of the Dines Chandra Santra group for detecting TNT by using fluorescence quenching chemistry is prepared by reacting substituted anthraquinone with sodium hydrosulfite, tetrabutylammonium bromide, sodium hydroxide aqueous solution and alkyl halide in a solvent, and the reaction conversion rate and the yield of the process are general. The Youhee Lim group adopts substituted anthraquinone to mix and react with zinc powder, sodium hydroxide aqueous solution and alkyl halide to obtain an anthracene ether product, and the reaction conversion rate and yield of the process are extremely low, and are only 18%.
Disclosure of Invention
The present invention solves the above problems by preparing 9, 10-dialkoxy (substituted) anthraquinones through a novel process.
The invention provides a preparation method of an organic optical material, which comprises the following steps: preparing 9, 10-dialkoxy (substituted) anthraquinone by adopting a one-pot method; the mixed metal powder used in the method is zinc powder and other metal powder; the other metal powder is iron powder, tin powder, aluminum powder or nickel powder.
The existing method for preparing 9, 10-dialkoxy (substituted) anthraquinone uses single metal powder, and its yield is very low, but said invention utilizes the synergistic effect of zinc powder and other metal powder to greatly raise its yield.
The invention preferably selects the mass ratio of the zinc powder to other metal powder as 3-99:1, when the mass ratio of the zinc powder to other metal powder is less than 3, the yield is low; when the mass ratio of the zinc powder to the other metal powder is more than 99, the chemical reaction proceeds slowly.
The concentration of the alkali solution used in the method is 10-80% in the invention, and the concentration of the alkali solution and the proportion of the mixed metal powder are simultaneously preferable in the invention, so that the speed of the chemical reaction is controlled.
The invention preferably comprises the following steps: anthraquinone or substituted anthraquinone, mixed metal powder, phase transfer catalyst, water, alkali solution and alkyl halide are prepared into 9, 10-dialkoxy (substituted) anthraquinone through one-pot process.
The substituent of the substituted anthraquinone is preferably C 1 -C 12 An alkyl, haloalkyl or halogen group.
In the invention, the phase transfer catalyst is preferably at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride.
In the invention, the alkali in the alkali solution is preferably at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide.
In the invention, preferably, the alkyl halide is at least one of halogenated ethane, halogenated propane, halogenated butane, halogenated pentane, halogenated hexane, halogenated heptane and halogenated octane, and the halogen in the alkyl halide is chlorine, bromine or iodine.
The invention preferably selects the anthraquinone or substituted anthraquinone, the mixed metal powder, the phase transfer catalyst, and the molar weight ratio of the alkali to the alkyl halide as 1:1-3:0.01-0.2:2-5:2.5-5.
The invention preferably adopts the following method: adding anthraquinone or substituted anthraquinone, mixed metal powder and a phase transfer catalyst into water, regulating the temperature to 40-75 ℃, uniformly mixing, dropwise adding an alkali solution, regulating the temperature to 50-80 ℃, dropwise adding alkyl halide, regulating the temperature to 50-80 ℃, reacting, adding a solvent when the content of the anthraquinone or substituted anthraquinone is less than 0.5%, uniformly mixing, separating, filtering, adding a crystallization solvent for crystallization, filtering and drying to obtain 9, 10-dialkoxy (substituted) anthraquinone; the solvent is at least one of aromatic hydrocarbon, aliphatic ketone, alcohol and water.
The invention has the beneficial effects that:
the preparation method provided by the invention is simple to operate, has low requirements on equipment, has the conversion rate of over 99 percent, the product purity of over 99 percent and the product yield of over 92 percent, and can be applied to industrial production in a large scale so as to meet the ever-increasing market demand.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but will not limit the invention in any way.
Example 1
Preparation of 9, 10-dibutoxyanthraquinone:
adding 41.6g of anthraquinone, 28.0g of zinc powder, 2.0g of nickel powder and 1.0g of tetrabutylammonium bromide into 85.0g of water, adjusting the temperature to 50 ℃, mixing uniformly, then adding 90.0g of 30% sodium hydroxide aqueous solution dropwise, adjusting the temperature to 65 ℃, then adding 170.0g of bromobutane dropwise, adjusting the temperature to 75 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying to obtain 61.2g of bright yellow green solid, namely 61.2g of 9, 10-dibutoxyanthraquinone, wherein the purity is 99.5%, and the yield is 95.0%.
Melting point 112.5-113.5 ℃.
1 H-NMR(CDCl 3 )1.08(t,6H),1.70(q,4H),2.05(m,4H),4.17(t,4H),7.51(d,4H),8.30(m,4H).
Example 2
Preparation of 9, 10-dibutoxyanthraquinone:
adding 41.6g of anthraquinone, 25.0g of zinc powder, 5.0g of iron powder and 10.0g of tetrabutylammonium bromide into 85.0g of water, adjusting the temperature to 50 ℃, uniformly mixing, then adding 60.0g of 45% sodium hydroxide aqueous solution dropwise, adjusting the temperature to 60 ℃, then adding 120.0g of bromobutane dropwise, adjusting the temperature to 65 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying to obtain 61.8g of bright yellow green solid, namely 61.9, 10-dibutoxyanthraquinone, wherein the purity is 99.1%, and the yield is 96.0%.
Example 3
Preparation of 9, 10-dibutoxyanthraquinone:
adding 41.6g of anthraquinone, 28.0g of zinc powder, 2.0g of iron powder and 5.0g of tetrabutylammonium chloride into 60.0g of water, adjusting the temperature to 50 ℃, uniformly mixing, then dropwise adding 105.0g of 25% sodium hydroxide aqueous solution, adjusting the temperature to 60 ℃, then dropwise adding 100.0g of chlorobutane, adjusting the temperature to 65 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying to obtain 62.5g of 9, 10-dibutoxyanthraquinone as a bright yellow green solid with the purity of 99.5% and the yield of 97.0%.
Example 4
Preparation of 9, 10-dibutoxyanthraquinone:
adding 41.6g of anthraquinone, 25.0g of zinc powder, 5.0g of tin powder and 5.0g of tetrabutylammonium chloride into 75.0g of water, adjusting the temperature to 50 ℃, uniformly mixing, then adding 90.0g of 30% sodium hydroxide aqueous solution dropwise, adjusting the temperature to 65 ℃, then adding 120.0g of bromobutane dropwise, adjusting the temperature to 65 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying to obtain 59.3g of 9, 10-dibutoxyanthraquinone as a bright yellow green solid, wherein the purity is 99.1%, and the yield is 92.0%.
Example 5
Preparation of 2, 6-dibromo-9, 10-dihexoanthraquinone:
adding 72.80g of 2, 6-dibromoanthraquinone, 28.50g of zinc powder, 1.50g of iron powder and 4.00g of tetrabutylammonium bromide into 67.00g of water, adjusting the temperature to 50 ℃, uniformly mixing, then dropwise adding 108.00g of 25% sodium hydroxide aqueous solution, adjusting the temperature to 65 ℃, then dropwise adding 204.80g of bromohexane, adjusting the temperature to 75 ℃, reacting for 60min, wherein the content of the 2, 6-dibromoanthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating liquid, filtering, removing most of methylbenzene to separate out a large amount of solid, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with an acetone/methanol mixed solution, and drying to obtain 100.93g of 2, 6-dibromo-9, 10-dihexyloxy anthraquinone, wherein the purity is 99.2%, and the yield is 94.0%.
Melting point 127-129 ℃.
Example 6
Preparation of 2, 6-dimethyl-9, 10-dibutoxyanthraquinone:
47.2g of 2, 6-dimethylanthraquinone, 29.0g of zinc powder, 1.0g of tin powder and 5.0g of tetrabutylammonium bromide are added into 100.0g of water, the temperature is adjusted to 50 ℃, the mixture is mixed evenly, 85.0g of 30% sodium hydroxide aqueous solution is dripped, the temperature is adjusted to 60 ℃, 170.0g of bromobutane is dripped, the temperature is adjusted to 70 ℃, the content of 2, 6-dimethylanthraquinone is less than 0.5% when the reaction is carried out for 60min, methylbenzene is added, the mixture is stirred for 1h, liquid separation and filtration are carried out, most of methylbenzene is removed, a large amount of solid is separated out, methanol is added, the temperature is reduced to 5 ℃, crystallization is carried out for 5h, filtration is carried out, a filter cake is washed by acetone/methanol mixed solution and is dried, and 66.7g of 2, 6-dimethyl-9, 10-dibutoxyanthraquinone is obtained, the purity is 99.0%, and the yield is 95.3%.
Melting point 114-116 ℃.

Claims (6)

1. A preparation method of 9, 10-dibutoxyanthraquinone is characterized in that: the method comprises the following steps: adding 41.6g of anthraquinone, 28.0g of zinc powder, 2.0g of nickel powder and 1.0g of tetrabutylammonium bromide into 85.0g of water, adjusting the temperature to 50 ℃, mixing uniformly, then adding 90.0g of 30% sodium hydroxide aqueous solution dropwise, adjusting the temperature to 65 ℃, then adding 170.0g of bromobutane dropwise, adjusting the temperature to 75 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying.
2. A preparation method of 9, 10-dibutoxyanthraquinone is characterized in that: the method comprises the following steps: adding 41.6g of anthraquinone, 25.0g of zinc powder, 5.0g of iron powder and 10.0g of tetrabutylammonium bromide into 85.0g of water, adjusting the temperature to 50 ℃, uniformly mixing, then dropwise adding 60.0g of 45% sodium hydroxide aqueous solution, adjusting the temperature to 60 ℃, then dropwise adding 120.0g of bromobutane, adjusting the temperature to 65 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying.
3. A preparation method of 9, 10-dibutoxyanthraquinone is characterized in that: the method comprises the following steps: adding 41.6g of anthraquinone, 28.0g of zinc powder, 2.0g of iron powder and 5.0g of tetrabutylammonium chloride into 60.0g of water, adjusting the temperature to 50 ℃, uniformly mixing, then dropwise adding 105.0g of 25% sodium hydroxide aqueous solution, adjusting the temperature to 60 ℃, then dropwise adding 100.0g of chlorobutane, adjusting the temperature to 65 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying.
4. A preparation method of 9, 10-dibutoxyanthraquinone is characterized in that: the method comprises the following steps: adding 41.6g of anthraquinone, 25.0g of zinc powder, 5.0g of tin powder and 5.0g of tetrabutylammonium chloride into 75.0g of water, adjusting the temperature to 50 ℃, uniformly mixing, then adding 90.0g of 30% sodium hydroxide aqueous solution dropwise, adjusting the temperature to 65 ℃, then adding 120.0g of bromobutane dropwise, adjusting the temperature to 65 ℃, reacting for 60min until the content of anthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating, filtering, removing most of methylbenzene, then precipitating a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying.
5. A preparation method of 2, 6-dibromo-9, 10-dihexoxantrone is characterized by comprising the following steps: the method comprises the following steps: adding 72.80g of 2, 6-dibromoanthraquinone, 28.50g of zinc powder, 1.50g of iron powder and 4.00g of tetrabutylammonium bromide into 67.00g of water, adjusting the temperature to 50 ℃, uniformly mixing, then dropwise adding 108.00g of 25% sodium hydroxide aqueous solution, adjusting the temperature to 65 ℃, then dropwise adding 204.80g of bromohexane, adjusting the temperature to 75 ℃, reacting for 60min, wherein the content of the 2, 6-dibromoanthraquinone is less than 0.5%, adding methylbenzene, stirring for 1h, separating liquid, filtering, removing most of methylbenzene to separate out a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with an acetone/methanol mixed solution, and drying.
6. A preparation method of 2, 6-dimethyl-9, 10-dibutoxyanthraquinone is characterized in that: the method comprises the following steps: adding 47.2g of 2, 6-dimethylanthraquinone, 29.0g of zinc powder, 1.0g of tin powder and 5.0g of tetrabutylammonium bromide into 100.0g of water, adjusting the temperature to 50 ℃, uniformly mixing, then adding 85.0g of 30% sodium hydroxide aqueous solution dropwise, adjusting the temperature to 60 ℃, then adding 170.0g of bromobutane dropwise, adjusting the temperature to 70 ℃, reacting for 60min, wherein the content of the 2, 6-dimethylanthraquinone is less than 0.5%, adding toluene, stirring for 1h, separating liquid, filtering, removing most of the toluene to separate out a large amount of solids, adding methanol, cooling to 5 ℃, crystallizing for 5h, filtering, washing a filter cake with acetone/methanol mixed solution, and drying.
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CN114195630B (en) * 2021-10-26 2023-04-25 湖南五江高科技材料有限公司 Synthesis method of photo-curing initiator 9, 10-dialkoxy anthracene
CN113880698B (en) * 2021-11-03 2022-03-25 济南周行医药科技有限公司 Preparation method of 9, 10-dibutoxyanthracene

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