WO2013114987A1 - Method of consistently producing diallylbisphenols - Google Patents
Method of consistently producing diallylbisphenols Download PDFInfo
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- WO2013114987A1 WO2013114987A1 PCT/JP2013/051040 JP2013051040W WO2013114987A1 WO 2013114987 A1 WO2013114987 A1 WO 2013114987A1 JP 2013051040 W JP2013051040 W JP 2013051040W WO 2013114987 A1 WO2013114987 A1 WO 2013114987A1
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- ethylene glycol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/18—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving halogen atoms of halogenated compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
Definitions
- the present invention relates to a method for producing diallyl bisphenols.
- Diallyl bisphenols are substances useful as color developers for heat-sensitive recording materials, and various production methods have been attempted. For example, bisphenol S (dihydroxydiphenyl sulfone) and allyl bromide are reacted to carry out an allylation reaction. After the obtained bisphenol S diallyl ether is taken out as a powder, the diallyl ether is heated to undergo rearrangement (Claisen rearrangement). A method for producing diallylated bisphenol S (3,3′-diallyl-4,4′-dihydroxydiphenylsulfone), which is reacted, is well known (Patent Document 1).
- Patent Document 2 describes a method for producing diallylated bisphenol S without taking out bisphenol S diallyl ether in the middle.
- the allylation reaction is carried out in water and / or an organic solvent, and the rearrangement reaction is carried out. It is disclosed to carry out in a solvent or without a solvent.
- the solvent used for the allylation is a low boiling point solvent
- the Claisen rearrangement reaction is carried out by replacing with no solvent or the solvent used for rearrangement.
- the Claisen rearrangement reaction is carried out without solvent.
- Patent Document 3 discloses that, in the Claisen rearrangement, when ethylene glycol is used as a solvent, a highly polar substance is generated, so that the reaction using the solvent is avoided as much as possible.
- the present invention has been made in view of the above problems, and has as its main object to provide high-quality diallyl bisphenols in high yield.
- the present invention provides the following method for producing diallyl bisphenols.
- Item 1 A method for consistently producing diallyl bisphenols from bisphenols, comprising the following steps (1) to (3): (1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt; (2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1), (3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction.
- Item 2. The method according to Item 1, comprising a step of recovering the cellosolve solvent in step (2) and / or step (3) and reusing at least a part of the recovered cellosolve solvent as a reaction solvent.
- Item 3. The method according to Item 1 or 2, wherein the cellosolve solvent is at least one selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.
- Item 4. The method according to any one of Items 1 to 3, wherein the bisphenol is bis (4-hydroxyphenyl) sulfone.
- Item 5. The method according to any one of Items 1 to 4, comprising a step of separating the by-product inorganic salt and neutralizing the obtained reaction solution in the step (2).
- reaction solvent can be recovered using the latent heat of vaporization of the solvent, so the solvent recovered in each process can be reused. It can be a rational and energy-saving manufacturing process.
- the method for consistently producing diallyl bisphenols from bisphenols is a method comprising the following steps (1) to (3). (1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt; (2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1), (3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction.
- Step (1) The above step (1) is preferably carried out by, for example, charging a cellosolve solvent, a starting bisphenol or an alkali metal salt thereof, if necessary, a basic metal compound and water into a closed container such as an autoclave. Is carried out by adding dropwise allyl halide under heating and reacting for a predetermined time.
- A is a single bond, —CH 2 —, —S—, —SO 2 —, —C (CH 3 ) 2 —, or
- the benzene nucleus may be further substituted.
- the compound represented by these is mentioned. Industrially, a compound having a hydroxyl group at the 4,4′-position is particularly important.
- bisphenol A 2,2′-bis (4-hydroxyphenyl) propane
- bisphenol C bis (4-hydroxyphenyl) cyclohexane
- bisphenol F bis ( 4-hydroxyphenyl) methane
- bisphenol S bis (4-hydroxyphenyl) sulfone
- bisphenol S bis (3-methyl-4-hydroxyphenyl) sulfone
- alkali metal salt of the bisphenol examples include those in which H in the —OH group is substituted with an alkali metal in the general formula (1).
- alkali metal sodium, potassium and the like are preferable.
- the alkali metal salt of bisphenols may be a monoalkali metal salt or a dialkali metal salt. When a dialkali metal salt of bisphenol is used as a starting material, a basic alkali metal compound described later may be unnecessary.
- the bisphenols represented by the general formula (1) and the alkali metal salts thereof used in the present invention may be in the form of powder or wet cake produced by a known method.
- the allyl halide in the present invention includes compounds in which substituents are introduced at the ⁇ , ⁇ and ⁇ positions of the allyl group.
- substituents include an alkyl group having 1 to 20 carbon atoms and an aromatic group.
- Specific examples of the allyl halide include allyl chloride, allyl bromide, allyl iodide, crotyl chloride, crotyl bromide, cinnamilk bromide, cinnamyl bromide and the like.
- cellosolve solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Of these, ethylene glycol monobutyl ether is preferred. These can also be mixed and used. Moreover, it may contain water.
- the basic alkali metal compound examples include alkali metal hydroxide compounds such as sodium hydroxide and potassium hydroxide, and alkali metal carbonate compounds such as sodium carbonate and potassium carbonate.
- the amount of the basic alkali metal compound used is usually 1.5 to 4 times mol, preferably 2 to 3 times mol for the bisphenol.
- a basic alkali metal compound may not be used. This basic alkali metal compound is used alone or in combination of two or more.
- the molar ratio of the bisphenol or its alkali metal salt to the allyl halide is in the range of 1: 2 to 1: 5, preferably in the range of 1: 2 to 1: 4.
- the reaction temperature is in the range of 50 to 150 ° C, preferably in the range of 80 to 120 ° C.
- the reaction time is in the range of 1 to 20 hours, preferably in the range of 2 to 10 hours.
- the pressure is in the range of 0 to 1 MPaG (G represents the gauge pressure), and preferably in the range of 0 to 0.3 MPaG.
- Step (2) is a step of separating the by-product inorganic salt from the reaction solution by a known method.
- a by-product inorganic salt for example, alkali metal halide
- the raw inorganic salt is dissolved and then allowed to stand, and then separated into a cellosolve solvent layer containing bisphenol diallyl ether and an aqueous layer containing by-product inorganic salt, and the aqueous layer is separated and removed.
- reaction solution containing a reaction product obtained by reacting a bisphenol or an alkali metal salt thereof with an allyl halide to produce a by-product inorganic substance.
- reaction system a reaction solution containing a reaction product obtained by reacting a bisphenol or an alkali metal salt thereof with an allyl halide to produce a by-product inorganic substance.
- allyl halide for example, allyl chloride
- alcohol which is a by-product from the reaction liquid.
- allyl alcohol and the like can be distilled off and separated.
- the distillate obtained here is further separated into an organic layer containing allyl halide and cellosolve solvent as unreacted raw materials, and an aqueous layer containing alcohols and water as by-products.
- the organic layer an organic layer containing an allyl halide and a cellosolve solvent
- the allylation reaction liquid from which the by-product inorganic salt has been separated can be used for the next rearrangement reaction.
- aqueous layer aqueous solution layer containing by-product inorganic salt
- organic layer cellosolve solvent layer containing bisphenol diallyl ether
- a small amount is contained in the organic layer. It is preferable to separate and remove the water, and then remove by-product inorganic salts precipitated in the organic layer before subjecting to the next rearrangement reaction.
- the by-product inorganic salt precipitated in the organic layer can be easily removed by hot filtration (hot filtration) or decantation.
- the aqueous layer and the separated organic layer are After performing the sum treatment, water contained in the organic layer may be separated and removed, and precipitated by-product inorganic salts may be removed according to the above procedure.
- a conventionally known method can be used as the neutralization treatment.
- a method of adding a neutralizing agent such as hydrochloric acid or dilute sulfuric acid to the organic layer and stirring at 0 to 100 ° C. for about 0.1 to 20 hours can be mentioned.
- the obtained organic layer (cellosolve solvent layer) is neutralized as necessary, and after removing water, by-product inorganic salts precipitated by hot filtration or the like are removed, Bisphenol diallyl ethers (for example, 4,4′-diallyloxydiphenyl sulfone) subjected to the rearrangement reaction of can be obtained.
- Bisphenol diallyl ethers for example, 4,4′-diallyloxydiphenyl sulfone
- Step (3) is a rearrangement reaction step, and is performed, for example, by reacting the organic layer obtained by separating the aqueous layer in the step (2) for a predetermined time under heating. .
- the rearrangement reaction temperature of the present invention is in the range of 150 to 250 ° C, and preferably in the range of 190 to 220 ° C.
- the reaction time is in the range of 0.1 to 100 hours, preferably in the range of 1 to 20 hours.
- rearrangement reaction can be carried out at normal pressure or under pressure.
- the rearrangement reaction can be carried out by adding an amine compound or an antioxidant as necessary.
- the amine compound is not particularly limited, and examples thereof include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylaminopyridine, benzotriazole, diethylenetriamine, and N, N-dimethylbenzylamine. be able to. These amine compounds may be used individually by 1 type, or may be used in combination of 2 or more type.
- the antioxidant is not particularly limited, and examples thereof include hydroquinone monomethyl ether, hydroquinone monoethyl ether, 3,5-di-t-butyl-4-hydroxytoluene, 2,2′-methylenebis (6-t-butyl).
- antioxidants such as 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,3′-thiodipropionate didodecyl, Sulfur antioxidants such as ditetradecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, triphenyl phosphite, diphenylisodecyl phosphite, tris phosphite (nonylphenyl) ) And the like. These antioxidants can be used alone or in combination of two or more.
- the cellosolve solvent as a reaction solvent can be recovered by distilling off under normal pressure and / or reduced pressure.
- the recovered cellosolve solvent can be recycled (reused) as it is to at least a part of it in the reaction system.
- the reaction mixture When the solvent is distilled off, the reaction mixture can be cooled to a temperature suitable for post-treatment by the latent heat of vaporization of the solvent.
- the reaction mixture cooled to a temperature suitable for the post-treatment step (about 0 to 150 ° C.) is added with an aqueous alkaline solution to dissolve allylated bisphenols, and a small amount of cellosolve solvent is stored. Can be left.
- the distilled cellosolve solvent can be recycled (reused) as it is at least in part to the reaction system.
- the reaction product from which the azeotrope has been removed is further purified by ordinary purification operations such as solvent extraction, washing, acid precipitation, recrystallization, and activated carbon purification. Thereby, high quality diallyl bisphenols can be obtained with a high yield.
- ethylene glycol monobutyl ether was measured, analyzed and calculated under the following conditions.
- Example 1 In an autoclave equipped with a stirrer, 3800 g of ethylene glycol monobutyl ether and 500 g of water were mixed and mixed, and 1000 g (4.0 mol) of 4,4′-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S) and 288 g (7. 2 mol) and 170 g (1.6 mol) of sodium carbonate were added successively. Next, 670 g (8.8 mol) of allyl chloride was added to form a sealed state, and the reaction was conducted by heating and stirring at 95 to 100 ° C. for 5 hours.
- bisphenol S 4,4′-dihydroxydiphenylsulfone
- the pressure was released, and the reaction solution was further heated to remove unreacted allyl chloride and the like.
- the distillate was separated into an upper layer and a lower layer.
- the upper layer (recovered solvent A) contained 165 g of ethylene glycol monobutyl ether.
- reaction mixture remaining in the kettle was cooled to 100 ° C., and then 1300 g of water was added and stirred to dissolve the by-product inorganic salt, followed by liquid separation to extract the lower layer (aqueous layer).
- the lower layer was 1900 g, and was an aqueous solution containing about 30% by weight of inorganic salts (sodium chloride) as main components and 0.3% by weight of ethylene glycol monobutyl ether. From the lower layer, 4,4'-diallyloxydiphenyl sulfone (hereinafter referred to as bisphenol S diallyl ether) was not detected.
- inorganic salts sodium chloride
- bisphenol S diallyl ether 4,4'-diallyloxydiphenyl sulfone
- the upper layer was an ethylene glycol monobutyl ether solution of bisphenol S diallyl ether having a water content of about 5% and a Na content of about 1000 ppm.
- the HPLC composition ratio was as follows: bisphenol S diallyl ether 97.1%, bisphenol S 0.2%, 4-hydroxyphenyl-4′-allyloxyphenyl sulfone (hereinafter referred to as bisphenol S monoallyl ether) 7%.
- the residue reaction solution after distillation was filtered hot to remove insolubles.
- the reaction solution (filtrate) after hot filtration contained 30 ppm of Na, and the yield calculated from the content of bisphenol S diallyl ether was 97%.
- the reaction solution (filtrate) after hot filtration, 0.13 g of N, N-dimethylaniline, and 0.13 g of hydroquinone monomethyl ether were charged into an autoclave and sealed at 205-215 ° C. in a sealed state (0.2 MPaG).
- the heat rearrangement reaction was performed for a time.
- the HPLC composition ratio (area percentage) of the reaction solution after the heat rearrangement reaction was 92.0% bis (3-allyl-4-hydroxyphenyl) sulfone, 2.9% monoallyl, 0.9% monorearrange, and others. It was 4.2%.
- the solvent in this reaction solution was cooled by distilling off ethylene glycol monobutyl ether under normal pressure and reduced pressure, and 3420 g was recovered.
- the recovered distillate (recovered solvent C) had a GC composition ratio (area percentage) of 99.5% ethylene glycol monobutyl ether.
- the residue reaction solution after the distillation was transferred to a four-necked flask, water was further added, activated carbon treatment was performed, and the target product was acidified using 25% by weight sulfuric acid.
- the obtained crystals were separated by filtration, washed with water, and dried to obtain 1114 g of a purified bis (3-allyl-4-hydroxyphenyl) sulfone product (yield based on bisphenol S: 84.4%).
- the purified bis (3-allyl-4-hydroxyphenyl) sulfone product had an HPLC composition ratio (area percentage) of 97.3% and a melting point of 154 to 155 ° C.
- Example 2 145 g of ethylene glycol monobutyl ether was added to a mixture of the total amount of the recovery solvents A to C in Example 1 and 182 g of the recovery solvent D, and bisphenol S, sodium hydroxide and sodium carbonate were sequentially added in the same manner as in Example 1. The same reaction and post-treatment were performed to obtain 1117 g of a bis (3-allyl-4-hydroxyphenyl) sulfone purified product (yield based on bisphenol S: 84.5%). The purified bis (3-allyl-4-hydroxyphenyl) sulfone product had an HPLC composition ratio (area percentage) of 97.1% and a melting point of 154 to 155 ° C.
- Example 3 In an autoclave equipped with a stirrer, 356 g of ethylene glycol monobutyl ether and 19 g of water were added and mixed. 150 g (0.657 mol) of 2,2′-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), hydroxylated Sodium 53 g (1.325 mol) and sodium carbonate 14 g (0.132 mol) were added sequentially. Next, 121 g (1.581 mol) of allyl chloride was added to form a sealed state, and the reaction was carried out by stirring with heating at 100 to 105 ° C. for 8 hours.
- bisphenol A 2,2′-bis (4-hydroxyphenyl) propane
- hydroxylated Sodium 53 g 1.325 mol
- sodium carbonate 14 g (0.132 mol
- the reaction solution (filtrate) after hot filtration was charged into an autoclave, and a heat rearrangement reaction was performed at 195 to 200 ° C. for 7 hours in a sealed state (0.1 MPaG). Thereafter, ethylene glycol monobutyl ether was distilled off at 150 ° C. under reduced pressure to obtain 166 g of 2,2′-bis (3-allyl-4-hydroxyphenyl) propane (hereinafter referred to as diallyl-bisphenol A) (relative to bisphenol A). Yield: 82%).
- the HPLC composition ratio (area percentage) of the obtained diallyl-bisphenol A was 92.0%.
- the upper layer (organic layer) was filtered hot to remove insolubles.
- the reaction liquid (filtrate) after hot filtration contained 1000 ppm of Na. This reaction liquid (filtrate) was cooled, crystallized, filtered and washed, and then dried to obtain 1200 g of bisphenol S diallyl ether as a powder. The yield was 90.9%.
- the reaction product was cooled, added with 1766 g of a 13 wt% aqueous sodium hydroxide solution, stirred and allowed to stand and separated. Then, the lower layer alkaline aqueous solution was charged into a four-necked flask and water was added, followed by activated carbon treatment. The target product was acidified using 25% by weight sulfuric acid. The obtained crystals were separated by filtration, washed with water, and then dried to obtain 1045 g of bis (3-allyl-4-hydroxyphenyl) sulfone purified product (yield based on bisphenol S: 79.2%). It was. The HPLC composition ratio (area percentage) of the obtained bis (3-allyl-4-hydroxyphenyl) sulfone refined product was 97.5%.
- the HPLC composition ratio (area percentage) of this reaction solution was as follows: bisphenol S diallyl ether 98.5%, bisphenol S 0.1%, 4-hydroxyphenyl-4′-allyloxyphenyl sulfone (bisphenol S monoallyl ether) 0. It was 5%.
- reaction solution was further heated, and the temperature was raised to 200 ° C. while removing unreacted allyl chloride and N, N-dimethylformamide as a solvent. Thereafter, a heat rearrangement reaction was performed at 200 to 220 ° C. for 6 hours.
- the HPLC composition ratio (area percentage) of the reaction solution after the heat rearrangement reaction was 35.3% bis (3-allyl-4-hydroxyphenyl) sulfone, 8.6% monoallyl, 3.5% monorearranged, etc.
- the component was 52.6%.
- Comparative Example 3 [Allylation Reaction with Solvent Used in Rearrangement Reaction of Comparative Example 1]
- 1900 g of Diana Fresia W-8 (paraffin oil) 1900 g of white kerosene, 500 g of water, 1000 g of 4,4′-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S), 4.0 mol of sodium hydroxide 288 g (7.2 mol) and sodium carbonate 170 g (1.6 mol) were sequentially added and mixed.
- the lower layer of the liquid separation was filtered to obtain a bisphenol S diallyl ether reaction product.
- the HPLC composition ratio (area percentage) of the reaction product was 73.9% bisphenol S diallyl ether, 3.4% bisphenol S, 4-hydroxyphenyl-4′-allyloxyphenyl sulfone (bisphenol S monoallyl ether) 10. Since the purity was as low as 2% and other components were 12.4%, the post-process was stopped.
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Abstract
Description
(1)ビスフェノール類又そのアルカリ金属塩とハロゲン化アリルとを、塩基性アルカリ金属塩の存在下又は不存在下で、セロソルブ系溶媒中で反応させる工程、
(2)工程(1)で得られた反応液から副生無機塩を分離する工程、
(3)工程(2)で得られた反応液を加熱し、転位反応を行う工程。 Item 1. A method for consistently producing diallyl bisphenols from bisphenols, comprising the following steps (1) to (3):
(1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt;
(2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1),
(3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction.
(1)ビスフェノール類又そのアルカリ金属塩とハロゲン化アリルとを、塩基性アルカリ金属塩の存在下又は不存在下で、セロソルブ系溶媒中で反応させる工程、
(2)工程(1)で得られた反応液から副生無機塩を分離する工程、
(3)工程(2)で得られた反応液を加熱し、転位反応を行う工程。 In the present invention, the method for consistently producing diallyl bisphenols from bisphenols is a method comprising the following steps (1) to (3).
(1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt;
(2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1),
(3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction.
1.工程(1)について
上記工程(1)は、例えば、オートクレーブ等の密閉容器に、セロソルブ系溶媒、出発物質のビスフェノール類またはそのアルカリ金属塩、必要に応じて塩基性金属化合物および水を仕込み、好ましくは加温下に、ハロゲン化アリルを滴下し、所定時間反応させることによって行われる。 Hereinafter, each step will be described.
1. Step (1) The above step (1) is preferably carried out by, for example, charging a cellosolve solvent, a starting bisphenol or an alkali metal salt thereof, if necessary, a basic metal compound and water into a closed container such as an autoclave. Is carried out by adding dropwise allyl halide under heating and reacting for a predetermined time.
で表される化合物が挙げられる。工業的には、4,4’-位に水酸基を有する化合物が特に重要である。
The compound represented by these is mentioned. Industrially, a compound having a hydroxyl group at the 4,4′-position is particularly important.
前記工程(2)は、公知の方法で、反応液から副生無機塩を分離する工程である。例えば、前記工程(1)で得られた反応生成物に、過飽和となって析出する副生無機塩(例えば、ハロゲン化アルカリ金属)を溶解するに十分な量の水又は温水を加えて、副生無機塩を溶解させ、次いで静置し、ビスフェノールジアリルエーテルが含まれるセロソルブ系溶媒層と、副生無機塩が含まれる水層と分液し、当該水層を分離除去することによって行われる。 2. Step (2) The step (2) is a step of separating the by-product inorganic salt from the reaction solution by a known method. For example, to the reaction product obtained in the step (1), an amount of water or warm water sufficient to dissolve a by-product inorganic salt (for example, alkali metal halide) that is supersaturated and precipitated is added. The raw inorganic salt is dissolved and then allowed to stand, and then separated into a cellosolve solvent layer containing bisphenol diallyl ether and an aqueous layer containing by-product inorganic salt, and the aqueous layer is separated and removed.
前記工程(3)は、転位反応工程であり、例えば、工程(2)で水層を分離して得られた有機層を、加熱下に、所定時間反応させることによって行われる。 3. Step (3) The step (3) is a rearrangement reaction step, and is performed, for example, by reacting the organic layer obtained by separating the aqueous layer in the step (2) for a predetermined time under heating. .
カラム:YMC-Pack ODS-A312(6.0φ×150mmL)
移動相:アセトニトリル/蒸留水=50/50
流 量:1.0ml/min.
検出器:UV 254nm
溶出時間:4,4’ -ジアリルオキシジフェニルスルホン=30分
ビス(3-アリル-4-ヒドロキシフェニル)スルホン=9分 Equipment: LC-10 system manufactured by Shimadzu Corporation Column: YMC-Pack ODS-A312 (6.0φ × 150mmL)
Mobile phase: acetonitrile / distilled water = 50/50
Flow rate: 1.0ml / min.
Detector: UV 254nm
Elution time: 4,4'-diallyloxydiphenylsulfone = 30 minutes Bis (3-allyl-4-hydroxyphenyl) sulfone = 9 minutes
検出器:UV 280nm(転位反応時)
溶出時間:2,2-ビス(4-アリルオキシフェニル)プロパン=14分
2,2’ -ビス(3-アリル-4-ヒドロキシフェニル)プロパン=9分 Mobile phase: acetonitrile / distilled water = 80/20
Detector: UV 280nm (during rearrangement reaction)
Elution time: 2,2-bis (4-allyloxyphenyl) propane = 14 minutes 2,2′-bis (3-allyl-4-hydroxyphenyl) propane = 9 minutes
カラム:TC-WAX (0.25mmφ×30m 膜厚0.25μm)
キャリアガス:窒素 30ml/min
カラム温度:90℃~250℃ 10℃/min
検出器:FID 250℃
溶出時間:エチレングリコールモノブチルエーテル=9分 Device: GC-2010 manufactured by Shimadzu Corporation
Column: TC-WAX (0.25mmφ × 30m film thickness 0.25μm)
Carrier gas: Nitrogen 30ml / min
Column temperature: 90 ° C to 250 ° C 10 ° C / min
Detector: FID 250 ° C
Elution time: ethylene glycol monobutyl ether = 9 minutes
攪拌機を備えたオートクレーブに、エチレングリコールモノブチルエーテル3800gおよび水500gを入れて混合し、4,4’-ジヒドロキシジフェニルスルホン(以下、ビスフェノールS)1000g(4.0モル)、水酸化ナトリウム288g(7.2モル)および炭酸ナトリウム170g(1.6モル)を順次加えた。次いで、アリルクロライド670g(8.8モル)を加えて密閉状態とし、95~100℃で5時間加熱攪拌して反応させた。 Example 1
In an autoclave equipped with a stirrer, 3800 g of ethylene glycol monobutyl ether and 500 g of water were mixed and mixed, and 1000 g (4.0 mol) of 4,4′-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S) and 288 g (7. 2 mol) and 170 g (1.6 mol) of sodium carbonate were added successively. Next, 670 g (8.8 mol) of allyl chloride was added to form a sealed state, and the reaction was conducted by heating and stirring at 95 to 100 ° C. for 5 hours.
実施例1における回収溶媒A~Cの全量と、回収溶媒D182gとの混合物に、145gのエチレングリコールモノブチルエーテルを追加し、ビスフェノールS、水酸化ナトリウムおよび炭酸ナトリウムを実施例1と同様に順次加え、同様に反応および後処理を行ったところ、ビス(3-アリル-4-ヒドロキシフェニル)スルホン精製品1117g(ビスフェノールSに対する収率:84.5%)を得た。得られたビス(3-アリル-4-ヒドロキシフェニル)スルホン精製品のHPLC組成比(面積百分率)は、97.1%、融点は154~155℃であった。 Example 2
145 g of ethylene glycol monobutyl ether was added to a mixture of the total amount of the recovery solvents A to C in Example 1 and 182 g of the recovery solvent D, and bisphenol S, sodium hydroxide and sodium carbonate were sequentially added in the same manner as in Example 1. The same reaction and post-treatment were performed to obtain 1117 g of a bis (3-allyl-4-hydroxyphenyl) sulfone purified product (yield based on bisphenol S: 84.5%). The purified bis (3-allyl-4-hydroxyphenyl) sulfone product had an HPLC composition ratio (area percentage) of 97.1% and a melting point of 154 to 155 ° C.
攪拌機を備えたオートクレーブに、エチレングリコールモノブチルエーテル356gおよび水19gを入れて混合し、2,2’-ビス(4-ヒドロキシフェニル)プロパン(以下、ビスフェノールA)150g(0.657モル)、水酸化ナトリウム53g(1.325モル)および炭酸ナトリウム14g(0.132モル)を順次加えた。次いで、アリルクロライド121g(1.581モル)を加えて密閉状態とし、100~105℃で8時間加熱攪拌して反応させた。 Example 3
In an autoclave equipped with a stirrer, 356 g of ethylene glycol monobutyl ether and 19 g of water were added and mixed. 150 g (0.657 mol) of 2,2′-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), hydroxylated Sodium 53 g (1.325 mol) and sodium carbonate 14 g (0.132 mol) were added sequentially. Next, 121 g (1.581 mol) of allyl chloride was added to form a sealed state, and the reaction was carried out by stirring with heating at 100 to 105 ° C. for 8 hours.
ビスフェノールSのアリル化を行い、得られた反応液(釜残)について、分液して下層(水層)を抜き出すところまでは、実施例1と同様に行った。 Comparative Example 1
Allylation of bisphenol S was carried out, and the reaction solution (bottle residue) thus obtained was separated in the same manner as in Example 1 until the lower layer (aqueous layer) was extracted.
四つ口フラスコに、N,N-ジメチルホルムアミド4000g、4,4’-ジヒドロキシジフェニルスルホン(以下、ビスフェノールS)1000g(4.0モル)、炭酸カリウム608g(4.4モル)を順次加え、混合した。次いで、p-トルエンスルホン酸アリルエステル1780g(8.4モル)を加えて、110~120℃で8時間加熱攪拌して反応させた。 Comparative Example 2 [Additional Examination of Example 2 in Patent Document 2]
To a four-necked flask, 4000 g of N, N-dimethylformamide, 1000 g (4.0 mol) of 4,4′-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S), and 608 g (4.4 mol) of potassium carbonate are sequentially added and mixed. did. Next, 1780 g (8.4 mol) of p-toluenesulfonic acid allyl ester was added, and the mixture was reacted by heating and stirring at 110 to 120 ° C. for 8 hours.
攪拌機を備えたオートクレーブに、ダイアナフレシアW-8(パラフィンオイル)1900g、白灯油1900g、水500g、4,4’-ジヒドロキシジフェニルスルホン(以下、ビスフェノールS)1000g(4.0モル)、水酸化ナトリウム288g(7.2モル)および炭酸ナトリウム170g(1.6モル)を順次加え混合し、次いで、相間移動触媒としてテトラブチルアンモニウムクロライド50g(0.18モル)、アリルクロライド670g(8.8モル)を加えて密閉状態とし、95~100℃で5時間加熱攪拌して反応させた。 Comparative Example 3 [Allylation Reaction with Solvent Used in Rearrangement Reaction of Comparative Example 1]
In an autoclave equipped with a stirrer, 1900 g of Diana Fresia W-8 (paraffin oil), 1900 g of white kerosene, 500 g of water, 1000 g of 4,4′-dihydroxydiphenylsulfone (hereinafter referred to as bisphenol S), 4.0 mol of sodium hydroxide 288 g (7.2 mol) and sodium carbonate 170 g (1.6 mol) were sequentially added and mixed. Then, 50 g (0.18 mol) of tetrabutylammonium chloride and 670 g (8.8 mol) of allyl chloride were used as a phase transfer catalyst. Was added to form a sealed state, and the mixture was reacted by stirring at 95-100 ° C. for 5 hours.
Claims (5)
- ビスフェノール類から、ジアリルビスフェノール類を一貫製造する方法であって、下記(1)~(3)の工程を含む方法。
(1)ビスフェノール類又そのアルカリ金属塩とハロゲン化アリルとを、塩基性アルカリ金属塩の存在下又は不存在下で、セロソルブ系溶媒中で反応させる工程、
(2)工程(1)で得られた反応液から副生無機塩を分離する工程、
(3)工程(2)で得られた反応液を加熱し、転位反応を行う工程。 A method for consistently producing diallyl bisphenols from bisphenols, comprising the following steps (1) to (3):
(1) reacting a bisphenol or an alkali metal salt thereof with an allyl halide in a cellosolve solvent in the presence or absence of a basic alkali metal salt;
(2) a step of separating a by-product inorganic salt from the reaction solution obtained in step (1),
(3) A step of heating the reaction liquid obtained in step (2) to perform a rearrangement reaction. - 工程(2)および/または工程(3)において、セロソルブ系溶媒を回収し、回収したセロソルブ系溶媒の少なくとも一部を、反応溶媒として再利用する工程を含む、請求項1に記載の方法。 The method according to claim 1, comprising a step of recovering the cellosolve solvent in step (2) and / or step (3) and reusing at least a part of the recovered cellosolve solvent as a reaction solvent.
- セロソルブ系溶媒が、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル及びエチレングリコールモノブチルエーテルからなる群より選択される少なくとも1種である、請求項1又は2に記載の方法。 The method according to claim 1 or 2, wherein the cellosolve solvent is at least one selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.
- ビスフェノール類が、ビス(4-ヒドロキシフェニル)スルホンである、請求項1~3のいずれかに記載の方法。 The method according to any one of claims 1 to 3, wherein the bisphenol is bis (4-hydroxyphenyl) sulfone.
- 工程(2)において、副生無機塩を分離し、得られた反応液を中和する工程を含む、請求項1~4のいずれか1項に記載の方法。 The method according to any one of claims 1 to 4, comprising a step of separating the by-product inorganic salt and neutralizing the obtained reaction liquid in the step (2).
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CN103880717A (en) * | 2014-03-21 | 2014-06-25 | 江苏傲伦达科技实业股份有限公司 | Preparation method of bis(3-allyl-4-hydroxy phenyl) sulfone and derivative thereof |
JP2015124208A (en) * | 2013-12-27 | 2015-07-06 | 日本化薬株式会社 | Method for producing 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone |
US11773207B2 (en) | 2019-01-07 | 2023-10-03 | Shikoku Chemicals Corporation | Thiol compound, method for synthesizing same, and uses for said thiol compound |
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CN106397283A (en) * | 2016-08-31 | 2017-02-15 | 金华盛纸业(苏州工业园区)有限公司 | Preparation method of temperature-sensitive developer 4,4'-sulfonylbis[2-(2-propenyl)]phenol |
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