o,o′-Diallylbisphenol A

Liquid

To an autoclave equipped with a stirrer, 356 g of ethylene glycol monobutyl ether and 19 g of water were added 150 g (0.657 mol) of 2, 2'-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 53 g (1.325 mol) of sodium hydroxide and 14 g (0.132 mol) of sodium carbonate were added in sequence. Subsequently, 121 g (1.581 mol) of allyl chloride was added and the mixture was reacted by heating at 100 to 105 DEG C for 8 hours while keeping the mixture in a sealed state. After the completion of the reaction, allyl chloride was distilled off in the same manner as in Example 1, and a water separation was performed. After neutralization, thermal treatment was performed to obtain an ethylene glycol monobutyl ether solution of bisphenol A diallyl ether. The reaction solution had an Na content of about 10 ppm. The HPLC composition ratio (area percentage) was 95.0percent for 2, 2-bis (4-allyl hydroxyphenyl) propane, 0.2percent for bisphenol A, and 4-hydroxyphenyl-4'-allyl hydroxyphenylpropane Bisphenol A monoallyl ether) was 2.2percent. The yield calculated from the content of bisphenol A diallyl ether was 95percent.The reaction solution (filtrate) after the thermal filtration was injected into an autoclave and the heating potential reaction was carried out at 195 to 200 in a closed state (0.1 MPaG) for 7 hours. Thereafter, ethylene glycol monobutyl ether was distilled off under reduced pressure at 150 to obtain 166 g of 2, 2'-bis (3-allyl-4-hydroxyphenyl) propane (hereinafter referred to as diallyl-bisphenol A) Yield: 82percent). The obtained diallyl-bisphenol A had a HPLC composition ratio (area percentage) of 92.0percent.47.56 g (0.22 mol) of DOPO 30.84 g (0.1 mol) (DABA) was added to a reaction vessel containing 400 mL of propanol under stirring.The temperature was raised to 75 C. After the DOPO and DABA were completely dissolved, 0.33 g (0.002 mol) of azobisisobutyronitrile initiator was added, stirred at a constant temperature, and after reacting for 24 hours, the reaction was terminated, and then desolvated and dried to obtain a middle portion. DDBACrude; under stirring, the crude intermediate DDBA is added to 100 mL of propanol, and the temperature is raised to 90 C until the DDBA crude product is completelyAfter dissolving, 300 mL of water is added, and the mixture is stirred and washed for 1 hour, and after repeated washing for 3 times, and then desolvated and dried, the purified mesh is obtained.Standard intermediate DDBA, yield 98.8%To a 500 ml flask, 22.61 g of a starting material, 29.75 ml of triethoxysilane, 337 mg of platinum oxide, and 60 ml of tetrahydrofuran were added and mixed, followed by stirring at 60 C. for 3 hours in an argon charged state. After the reaction, the crude product thus obtained was filtered using a celite filter, and solvents were removed using an evaporator to obtain a bisphenol A compound including an alkoxysilyl group as a final product. The reaction scheme and the NMR data of the final product thus obtained are as follows.1H NMR (400 MHz, DMSO): delta=0.53 (t, J=8.0 Hz, 4H), 1.11 (t, J=4.0 Hz, 18H), 1.51-1.57 (m, 10H), 2.44-2.48 (m, 4H), 3.70 (dd, J=8.0 Hz, 12H), 6.62-6.68 (m, 2H), 6.78-6.85 (m, 4H), 8.94 (br, 2H).A solution containing 1380 g (10.0 mol) of potassium carbonate (Nippon Soda Co. , Ltd.) dissolved in 1250 g of pure water, 800 g (2.62 mol) of 4, 4?-(dimethylmethylene)bis[2-(2-propenyl)phenol] represented by formula (3) (Daiwa Fine Chemicals Co., Ltd.) and 520 g (5.00 mol, solid) of sodium carbonate (Kanto Chemical Co., Ltd.) were charged into a 5 L 3-neck round bottom flask followed by replacing the air inside the reaction vessel with nitrogen gas and heating to 85 C. Under the flow of nitrogen gas, 2200 g (21.9 mol) of allyl acetate (Showa Denko 26.2 g (100 mmol) of triphenylphosphine (Hokko Chemical Industry Co., Ltd.) and 846 mg (0.200 mmol, as Pd atoms) of 50% aqueous 5% Pd/C-STD type (N.E. Chemcat Corp.) were added, and after raising the temperature to 105 C. and allowing to react for 4 hours in a nitrogen gas atmosphere, 220 g (2.19 mol) of allyl acetate were additionally added followed by continuing to heat for 12 hours. Following completion of the reaction and after allowing the reaction system to cool to room temperature, pure water was added until all of the precipitated salt dissolved to separate the reaction solution. The organic phase was separated followed by distilling off the organic solvent (70 C., 50 mmHg, 2 hours). After adding pure water (2000 g), 2000 g of toluene were added, and after confirming that a white sediment no longer precipitated while holding the temperature at 80 C. or higher, Pd/C was recovered by filtration. (using 1 micron membrane filter (KST-142-JA filter manufactured by Advantech Co., Ltd.) under pressure (0.3 MPa)). This filter residue was washed with 1000 g of toluene together with separating the aqueous layer. The organic layer was washed twice with 2000 g of pure water at 50 C. and the aqueous layer was confirmed to be neutral. After separating the organic layer, the organic layer was concentrated under reduced pressure to obtain a brown liquid having for the main component thereof 4, 4?-(dimethylmethylene)bis[2-(2-propenyl)phenyl diallyl ether] represented by formula (4) (936 g, 2.41 mmol, yield: 92.0%). As a result of measuring this brown liquid by 1H-NMR, it was confirmed to contain the compound represented by formula (4) as the main component thereof. Measurement data assigned to the compound represented by formula (4) is as shown below. 1H-NMR {400 MHz, CDCl3, 27 C.}, delta1.66 (6H, s, CH3) delta3.39 (4H, d, PhCH2CH'CH2) , delta4.95-5.55 (4H, m, PhCH2CH'CH2), delta5.25 d, PhOCH2CH'CHH), delta5.42 (2H, d, PhOCH2CH'CHH), delta5.25 (4H, m, PhOCH2CH'CH2, PhCH2CH'CH2), delta6.73 (d, 2H, aromatic), delta6.90-7.08 (m, 2H, aromatic.), delta7.13-7.40 (2H, m, aromatic).Into a 500 mL three-necked round bottom flask, Potassium carbonate (manufactured by Nippon Soda Co., Ltd.)A solution of 138 g (1.00 mol) dissolved in 125 g of pure water, Represented by the formula (3)4, 4 '- (dimethylmethylene) bis [2- (2-propenyl) phenol](Manufactured by Yamato Kasei Co., Ltd.)80.6 g (262 mmol), And sodium carbonate (manufactured by Kanto Kagaku Co., Ltd.)52.0 g (0.500 mol, as a solid) were charged, The reactor was purged with nitrogen and heated to 85 C. Under nitrogen stream, 220 g (2.19 mol) of allyl acetate (manufactured by Showa Denko KK)2.62 g (10.0 mmol) of triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd.)And 50% water content 5% - Pd / C - STD type(Manufactured by NEC Chemcat Corporation)84.6 mg (0.0200 mmol) was added, In a nitrogen atmosphere, After raising the temperature to 105 C. and reacting for 4 hours, 22.0 g (0.219 mol) of allyl acetate was added additionally, Heating was continued for 12 hours. After completion of the reaction, the reaction system was cooled to room temperature, and then pure water was added until all of the precipitated salt was dissolved, and liquid separation treatment was carried out.The organic layer was separated and the organic solvent (70 C., 50 mmHg, 2 hours) was distilled off.After adding pure water (200 g), 200 g of toluene was added, After confirming that no white precipitate was precipitated by keeping at a temperature of 80 C. or higher, Pd / C was recovered by filtration (1 micron membrane filter (pressurized (0.3 MPa) using KST-142-JA manufactured by Advantec Corporation). The filter cake was washed with 100 g of toluene, and the aqueous layer was separated.The organic layer was washed twice with 200 g of pure water at 50 C. or higher, and it was confirmed that the aqueous layer was neutral.After separating the organic layer, it is concentrated under reduced pressure to obtain a compound represented by the formula (4)4, 4 '- (dimethylmethylene)Bis [2- (2-propenyl)Phenyl diallyl ether]Brown liquid containing as a main component(93.6 g, 241 mmol, 92.0% yield).20 g of 2, 2'-diallylbisphenol A (1-0), 100 ml of THF and 50 g of pyridine were placed in a two-necked flask at room temperatureand stirred. Then, 14.6 g of acetic anhydride was added thereto and stirred for 1 hour. After completion of the reaction, thesolvent was removed, 300 ml of ethyl acetate was added, and the mixture was worked up with H2O. MgSO4 was added to theorganic layer to remove remaining H2O, followed by filtration with a Celite filter and drying to obtain an intermediate product(1-1) having an ester group and a hydroxy group ratio of 1: 1. NMR data of the obtained intermediate product (1-1) is as followsTo an autoclave equipped with a stirrer, 356 g of ethylene glycol monobutyl ether and 19 g of water were added 150 g (0.657 mol) of 2, 2'-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 53 g (1.325 mol) of sodium hydroxide and 14 g (0.132 mol) of sodium carbonate were added in sequence. Subsequently, 121 g (1.581 mol) of allyl chloride was added and the mixture was reacted by heating at 100 to 105 DEG C for 8 hours while keeping the mixture in a sealed state. After the completion of the reaction, allyl chloride was distilled off in the same manner as in Example 1, and a water separation was performed. After neutralization, thermal treatment was performed to obtain an ethylene glycol monobutyl ether solution of bisphenol A diallyl ether. The reaction solution had an Na content of about 10 ppm. The HPLC composition ratio (area percentage) was 95.0% for 2, 2-bis (4-allyl hydroxyphenyl) propane, 0.2% for bisphenol A, and 4-hydroxyphenyl-4'-allyl hydroxyphenylpropane Bisphenol A monoallyl ether) was 2.2%. The yield calculated from the content of bisphenol A diallyl ether was 95%.The reaction solution (filtrate) after the thermal filtration was injected into an autoclave and the heating potential reaction was carried out at 195 to 200 in a closed state (0.1 MPaG) for 7 hours. Thereafter, ethylene glycol monobutyl ether was distilled off under reduced pressure at 150 to obtain 166 g of 2, 2'-bis (3-allyl-4-hydroxyphenyl) propane (hereinafter referred to as diallyl-bisphenol A) Yield: 82%). The obtained diallyl-bisphenol A had a HPLC composition ratio (area percentage) of 92.0%.A 100-mL recovery flask was charged with 20 g of dioxane and 5 g of diallyl bisphenol A, and the mixture was stirred at room temperature. When the mixture became a homogeneous solution, 2.5 g of hexamethyldisilazane was added and the reaction was terminated in two hours. After the solvent and the reaction residues were removed, the presence of the peak derived from trimethylsilyl group and the absence of the peak derived from hydroxyl group were confirmed by 1H-NMR. Thus, a diallyl bisphenol A (reactant (2), 6.5 g) whose hydroxyl groups were protected with trimethylsilyl groups was obtained. The chemical formula of the reactant (2) is shown below.

Intermediates

Molecular Weight:308.4
XLogP3:6.1
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:6
Exact Mass:308.177630004
Monoisotopic Mass:308.177630004
Topological Polar Surface Area:40.5
Heavy Atom Count:23
Complexity:365
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes