A method for preparing 9,9-dioctyl-2-fluoreneboric acid

Abstract

The present invention relates to a method for preparing 9,9-dioctyl-2-fluorene boric acid, industrial 2-bromofluorene, sodium tert-butoxide, n-hexane, 1-bromooctane and activating agent are added to a reaction bottle, reacted at room temperature for 1-3 hours, and then n-hexane, 1-bromooctane and activating agent are extracted in turn by vacuum distillation, and an equal amount of n-hexane solution is added again; the temperature is cooled to 40-80°C, n-butyl lithium is added, and stirred for 0.5-1 hour; trimethyl borate is added again, and stirred for 1-2 hours; after completion of the reaction, the temperature is controlled to be lower than 20-0°C, hydrochloric acid solution is dripped, reacted for 1-4 hours, and then warmed to 0-20°C for reaction for 3-6 hours; liquid separation, organic layer is washed with saturated salt water, and water layer is extracted 3 times with n-hexane; after the organic layers are mixed, the solvent is recovered by vacuum distillation; the filter cake is washed with deionized water to pH=6-7, and the finished product is obtained after drying. The present invention meets the production requirements of economic efficiency and high yield.

Description

Technical Field

[0001] The invention relates to the field of chemical industry, and in particular to a method for preparing 9,9-dioctyl-2-fluoreneboric acid. Background Art

[0002] With the development of science and technology, photovoltaic devices and OLED materials have become a hot topic in the field of electronics and optoelectronics. 9,9-Dioctyl-2-fluorene borate is one of the important intermediates in the preparation of optical materials. At present, the more common preparation methods are costly and not conducive to large-scale industrial production. Summary of the invention

[0003] The invention provides a method for preparing 9,9-dioctyl-2-fluoreneboric acid. The method is simple and meets the production requirements of economic efficiency and high yield.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A method for preparing 9,9-dioctyl-2-fluorene borate comprises the following steps:

[0006] 1) Add industrial 2-bromofluorene, sodium tert-butoxide, n-hexane, 1-bromooctane and an active agent to a reaction bottle respectively, stir evenly, react at 20-30° C. for 1-3 hours, extract n-hexane, 1-bromooctane and an active agent in turn by vacuum distillation, and add an equal amount of n-hexane solution again;

[0007] 2) Cooling to -40 to -80°C, adding n-butyl lithium (1.6M n-hexane solution) dropwise, stirring for 0.5 to 1 hour; then adding trimethyl borate dropwise, stirring for 1 to 2 hours; after the reaction is completed, controlling the temperature of the reaction system to be lower than -20 to 0°C, adding hydrochloric acid solution dropwise, continuing the reaction for 1 to 4 hours, and then gradually raising the temperature to 0 to 20°C and reacting for 3 to 6 hours;

[0008] 3) Separate the liquids, wash the organic layer with saturated brine, extract the aqueous layer with n-hexane three times to collect organic matter, and treat the aqueous layer as waste water after extraction;

[0009] 4) After mixing the organic layers, the solvent was recovered by distillation under reduced pressure;

[0010] 5) The filter cake is washed with deionized water until the pH value is 6-7, and then dried to obtain the finished product of 9,9-dioctyl-2-fluorene boric acid.

[0011] In the above step 1), the active agent is one of 1-aminododecane and tetrapropylammonium hydroxide.

[0012] In the above step 1), the mass ratio of various components is 2-bromofluorene: sodium tert-butoxide: n-hexane: 1-bromooctane: activator = 1: (0.8-1.4): (4-10): (1.6-2.7): (0.01-0.03).

[0013] In the above step 2), the mass ratio of various components is: 2-bromofluorene: n-butyl lithium: trimethyl borate: hydrochloric acid = 1: (2-2.5): (0.5-2): (4-5).

[0014] The hydrochloric acid is a 1M hydrochloric acid solution.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] 1) The reaction rate is faster and the reaction temperature is easier to achieve.

[0017] 2) The existing reaction system is easy to operate, has a short reaction cycle, and has cost advantages, meeting the production requirements of economic efficiency and high yield.

[0018] 3) The liquid chromatography purity of the product is higher than 99%, and the yield of 9,9-dioctyl-2-fluoreneboric acid is higher than 85%, which is more suitable for industrial production. DETAILED DESCRIPTION

[0019] The specific implementation mode of the present invention will be further described below in conjunction with embodiments:

[0020] Embodiment 1:

[0021] In a 1L reaction bottle with heating, cooling, stirring, thermometer, and reflux condenser, 40g of 2-bromofluorene, 56g of sodium tert-butoxide, 200g of n-hexane, 90g of 1-bromooctane, and 0.5g of 1-aminododecane were added in sequence, nitrogen protection was introduced and stirred until dissolved, and the reaction was carried out at room temperature for 2 hours. Then, n-hexane, 1-bromooctane and 1-aminododecane were extracted by vacuum distillation, and 200g of n-hexane solution was added again. The temperature was lowered to -78°C, 100g of n-butyl lithium (1.6M n-hexane solution) was added dropwise, and stirred for 0.5 hour. 35g of trimethyl borate was added dropwise and stirred for 1 hour. After the reaction was completed, the temperature of the reaction system was controlled to -20°C, 180g of hydrochloric acid solution (1M) was added dropwise, the reaction was continued for 1 hour, and then the temperature was gradually raised to 20°C for reaction for 4 hours. Liquid separation, the organic layer was washed with a small amount of saturated brine, and the water layer was extracted 3 times with a small amount of n-hexane. After the organic layers are mixed, the solvent is recovered by vacuum distillation. The filter cake is washed with deionized water until the pH value is 6-7, and the 9,9-dioctyl-2-fluorene boric acid product is obtained after drying, with a purity of 99.1%.

[0022] Embodiment 2:

[0023] In a 1L reaction bottle equipped with heating, cooling, stirring, thermometer, and reflux condenser, 40g of 2-bromofluorene, 32g of sodium tert-butoxide, 160g of n-hexane, 65g of 1-bromooctane, and 0.4g of 1-aminododecane were added in sequence, nitrogen protection was introduced and stirred until dissolved, and the reaction was carried out at room temperature for 3 hours. Then, n-hexane, 1-bromooctane and 1-aminododecane were extracted by vacuum distillation, and 160g of n-hexane solution was added again. The temperature was lowered to -50°C, 80g of n-butyl lithium (1.6M n-hexane solution) was added dropwise, and stirred for 0.5 hours. 20g of trimethyl borate was added dropwise and stirred for 1 hour. After the reaction was completed, the temperature of the reaction system was controlled to 0°C, 180g of hydrochloric acid solution (1M) was added dropwise, and the reaction was continued for 1 hour, and then the temperature was gradually raised to 20°C for reaction for 6 hours. Liquid separation, the organic layer was washed with a small amount of saturated brine, and the water layer was extracted 3 times with a small amount of n-hexane. After the organic layers are mixed, the solvent is recovered by vacuum distillation. The filter cake is washed with deionized water until the pH value is 6-7, and the 9,9-dioctyl-2-fluorene boric acid product is obtained after drying, with a purity of 98.6%.

[0024] Embodiment 3:

[0025] In a 1L reaction bottle equipped with heating, cooling, stirring, thermometer, and reflux condenser, 40g of 2-bromofluorene, 45g of sodium tert-butoxide, 180g of n-hexane, 80g of 1-bromooctane, and 1g of tetrapropylammonium hydroxide were added in sequence, nitrogen was introduced for protection and stirred until dissolved, and the reaction was carried out at room temperature for 1 hour. Then, n-hexane, 1-bromooctane and 1-aminododecane were extracted by vacuum distillation, and 180g of n-hexane solution was added again. The temperature was lowered to -78°C, 90g of n-butyl lithium (1.6M n-hexane solution) was added dropwise, and stirred for 0.5 hour. 40g of trimethyl borate was added dropwise and stirred for 1 hour. After the reaction was completed, the temperature of the reaction system was controlled to -20°C, 200g of hydrochloric acid solution (1M) was added dropwise, the reaction was continued for 1 hour, and then the temperature was gradually raised to 20°C for reaction for 4 hours. Liquid separation, the organic layer was washed with a small amount of saturated brine, and the aqueous layer was extracted 3 times with a small amount of n-hexane. After the organic layers are mixed, the solvent is recovered by vacuum distillation. The filter cake is washed with deionized water until the pH value is 6-7, and the 9,9-dioctyl-2-fluorene boric acid product is obtained after drying, with a purity of 99.4%.

[0026] Embodiment 4:

[0027] In a 1L reaction bottle equipped with heating, cooling, stirring, thermometer, and reflux condenser, 40g of 2-bromofluorene, 35g of sodium tert-butoxide, 170g of n-hexane, 74g of 1-bromooctane, and 1.2g of tetrapropylammonium hydroxide were added in sequence, nitrogen was introduced for protection and stirred until dissolved, and the reaction was carried out at room temperature for 1.5 hours. Then, n-hexane, 1-bromooctane and 1-aminododecane were extracted by vacuum distillation, and 170g of n-hexane solution was added again. The temperature was lowered to -50°C, 90g of n-butyl lithium (1.6M n-hexane solution) was added dropwise, and stirred for 0.5 hours. 30g of trimethyl borate was added dropwise and stirred for 1 hour. After the reaction was completed, the temperature of the reaction system was controlled to 0°C, 160g of hydrochloric acid solution (1M) was added dropwise, and the reaction was continued for 1 hour, and then the temperature was gradually raised to 20°C for reaction for 6 hours. Liquid separation, the organic layer was washed with a small amount of saturated brine, and the aqueous layer was extracted 3 times with a small amount of n-hexane. After the organic layers are mixed, the solvent is recovered by vacuum distillation. The filter cake is washed with deionized water until the pH is 6-7, and then dried to obtain the finished product of 9,9-dioctyl-2-fluorene boric acid with a purity of 99%.

Claims

1. A method for preparing 9,9-dioctyl-2-fluoreneboric acid, characterized in that: The following steps are involved: 1) Add industrial 2-bromofluorene, sodium tert-butoxide, n-hexane, 1-bromooctane and an active agent to a reaction flask respectively, stir evenly, react at 20-30° C. for 1-3 hours, extract n-hexane, 1-bromooctane and an active agent in turn by vacuum distillation, and add an equal amount of n-hexane solution again; 2) Cooling to -40 to -80°C, adding 1.6M n-butyl lithium n-hexane solution dropwise, stirring for 0.5 to 1 hour; then adding trimethyl borate dropwise, stirring for 1 to 2 hours; After the reaction is completed, the temperature of the reaction system is controlled to be lower than -20 to 0°C, and hydrochloric acid solution is added dropwise, and the reaction is continued for 1 to 4 hours, and then the temperature is gradually raised to 0 to 20°C and the reaction is carried out for 3 to 6 hours; 3) Separate the liquids, wash the organic layer with saturated brine, extract the aqueous layer with n-hexane three times to collect organic matter, and treat the aqueous layer as waste water after extraction; 4) After mixing the organic layers, the solvent was recovered by distillation under reduced pressure; 5) washing the filter cake with deionized water until the pH value is 6-7, and then drying to obtain the finished product of 9,9-dioctyl-2-fluorene boric acid; In the above step 1), the active agent is 1-aminododecane; In the above step 1), the mass ratio of various components is 2-bromofluorene: sodium tert-butoxide: n-hexane: 1-bromooctane: active agent = 1: (0.8-1.4): (4-10): (1.6-2.7): (0.01-0.03); In the above step 2), the mass ratio of various components is: 2-bromofluorene: n-butyl lithium: trimethyl borate: hydrochloric acid = 1: (2-2.5): (0.5-2): (4-5).

2. A method for preparing 9,9-dioctyl-2-fluoreneboric acid according to claim 1, characterized in that: The hydrochloric acid is a 1M hydrochloric acid solution.