Tris(4-hydroxyphenyl)ethane

OtherSolid

DryPowder; OtherSolid

Synthesis method:The reactor was charged with 54.0 moles of phenol and 100 partsGrams of zinc chloride, Stirring to make it mixed evenly, Followed by slow addition over a period of 40 minutes6.5 mol of p-hydroxyacetophenone, After warming up to join Under the conditions of temperature and 60 60 min100 ml of concentrated hydrochloric acid, After the addition, the reaction was stirred for 8 h.After stirring, the temperature was lowered to 20 ° C, Dichloroethane was added, After sufficiently stirring again, filter, 55 vacuum drying 6hThe crude THPE product 1811 grams.The purity of the crude product95.0percent and yield 91.1percent. Purification method:1000 g of the crude product prepared above was added2000 ml of methanol, Heating completely dissolved, cool down, Slowly add1600 ml of water, Stirred at room temperature for 50 min to give pale yellow product;filter, drying.The dried product was dissolved in 1200 ml of methanol, After complete dissolution by heating, Add activated carbon decolorization, Filtered, the solvent evaporated, The resulting solid;The obtained solid was dissolved in 1000 ml of methanol, A solution of a mixture of sodium borohydride (5 g) and sodium sulfite (35 g) was slowly added, Light yellow powder gradually precipitation, The resulting solid was filtered, Vacuum drying 10 h at 25 ° C to give 913 g of product;The yield was 91.3percentHPLC analysis purity 99.5percent.In this example, THPE was prepared from 4-hydroxyacetophenone, phenol, mercaptopropionic acid, and methane sulfonic acid. Phenol (200 grams (g)) was charged into a 500 milliliters (ml) 4-necked round bottom flask equipped with a mechanical stirrer, thermometer pocket, and a water-cooled reflux condenser with a calcium chloride guard and an air leak tube. The flask was then heated to 55 C. and maintained under nitrogen atmosphere, while stirring. Next, p-hydroxyacetophenone (34 g) and 3-mercaptopropionic acid (5.5 g) were added. The methane sulfonic acid (14.81 g) was then added in a drop wise manner over about a thirty minute period. The reaction mixture was maintained at 55 C. under nitrogen atmosphere for 20 hours. The reaction mixture was then cooled room temperature (RT, 24 C.) and the nitrogen flow was stopped. The reactants of the flask were transferred into a 1 liter (L) beaker containing ethylene dichloride (600 ml) and stirred for 2 hours. The solids were filtered to get a crude product weighing approximately 58 g. The crude product was then subjected to a purification process as described below. The purification process included stirring the crude reaction product into a methanol-water mixture (40:60 volume be volume, 120 ml) for 0.5 hours. Next the solids were filtered off, and the process was repeated with additional methanol-water (80 ml). The solids so obtained were then dissolved in methanol (120 ml). Sodium borohydride (NaBH4, 150 milligrams) was added to this mixture, followed by stirring for half an hour. The solution was then treated with 1 gram of charcoal and subsequently filtered. 280 ml of water containing sodium borohydride (0.0125percent weight by volume) was added to the filtrate over a period of 2 hours under nitrogen atmosphere. Another 120 ml of water containing 0.0125percent w/v of sodium borohydride was added to this mixture all at once and stirred for 2 hours. The solids were then filtered and washed with 100 ml of 20percent volume by volume of methanol in water. The purified solids were dried at 60 C. under vacuum to constant weight to provide 53 g of product. The ethylene dichloride used to isolate the solids was recovered by distilling the reaction mixture while maintaining the reaction temperature at 50-55 C., under vacuum, initially at 180 mm and at the end at 60 mm. The residue so obtained was recycled in the next batch; In this example, the residue obtained in was recycled. Recycle 2a: The residue was used in the next batch with phenol (46.4 g), p-hydroxyacetophenone (34 g), 3-mercaptopropionic acid (2.44 g) and methane sulfonic acid (8.9 g). The reaction was carried out in a similar manner as the original batch to get a purified THPE (58.98 g). Recycle 2b: The residue obtained from the filtrate of recycle 1a was reacted in a similar manner with phenol (59 g), p-hydroxyacetophenone (34 g), 3-mercaptopropionic acid (2.44 g) and methane sulfonic acid (8.9 g) to provide a purified THPE (56.03 g). Unreacted phenol was obtained by distilling the filtrate under vacuum (distillation temperature 61-62 C. at 0.4 mm of Hg). The results of Example 1, and the recycle steps are tabulated in Table 2 below; EXAMPLE 3 In this example, THPE was prepared in accordance with using the phenol recovered from Example 1. The results are tabulated in Table 2 below.EXAMPLES 8-10 These examples provide a method for preparing THPE in the absence of a co-catalyst. The reaction was carried out in a similar manner as described in above using A-121 2percent cross linked ion exchange resin at a temperature of 75° C.in the absence of a co-catalyst. The reaction contents, reaction parameters, and HPLC analysis results are included in Table 4 below. TABLE 4 HPLC Analysis Catalyst Phenol Time THPE BPA Example (A-121) (g) (g) PD (g) (hours) Yield percent Yield percent 8 2.48 47 2.503 46 47.80 40.69 9 4.95 47 2.503 24 48.82 60.21 10 7.43 47 2.503 24 42.59 72.82EXAMPLE 2-7 These examples provide a method for the preparation HPE as generally outlined in Example 1. Examples 2-5 employed 3-MPSA as the talyst whereas Examples 6-7 utilized 3-MPA. The reaction contents, time, and s are included in Table 3 below. All the reactions were carried out at a erature of about 65° C. The weight percent of the co-catalyst and catalyst used is d on the total weight of the reaction mixture, i.e., total weight of phenol and PD. TABLE 3 HPLC analysis results Phenol Co-catalyst IER Resin Time THPE BPA Ex. PD (g) (g) (g) A-121 (g) (hours) yield (percent) yield (percent) 2 4.1 50 0.54 4.33 2 7.43 2.27 3-MPSA 4 0.53 4.27 20 40.91 62.68 22 46.34 67.87 24 45.66 67.15 26 51.96 70.76 46 57.47 71.18 48.5 57.16 71.16 3 4.1 50 1.08 4.89 2 2.08 1.11 3-MPSA 4 0.39 2.05 20 46.24 62.67 22 49.65 64.94 24 48.07 66.19 26 49.30 66.32 28 48.04 65.54 48.5 54.65 67.73 4 4.1 50 1.62 4.89 2 4.19 2.09 3-MPSA 4 14.84 9.88 20 46.22 66.37 26 44.90 64.92 28.5 49.36 66.97 28.5 49.85 67.15 5 2.7 50 0.54 3.20 20 57.60 70.49 3-MPSA 22 56.55 71.09 26 60.79 74.41 44 58.36 74.98 46 58.79 72.86 46 59.00 73.06 6 2.5 47 0.79 4.95 24 49.05 78.15 3-MPA 7 2.5 47 0.79 9.90 18 45.94 80.92 3-MPA EXAMPLES 12-20 In these examples, THPE adduct was prepared using the method described in Example 6 above. The reaction contents and reaction parameters are tabulated in Table 5 and the results are tabulated in Table 6 below. Table 6 includes the HPLC analysis results of the amount of THPE, BPA and phenol in the adduct and in the effluent. TABLE 5 Temperature Wt. of Reaction Contents in ° C. THPE BPA THPE Phenol Homogenous Adduct taken Example in g in g in g Solution Formation (g) 12 11.4 15.4 28.2 160 135-139 15.3 13 11.4 15.4 37.6 150 126-128 15.3 14 11.4 15.3 56.5 135 103 15.3 15 13.7 18.4 112.9 130 55 18.4 16 - 15.4 28.2 165 143-145 15.4 17 - 15.4 37.6 150 133 15.4 18 - 61.2 150.4 150 135 61.2 19 - 7.65 28.2 135 117 7.6 20 - 7.65 37.6 130 95-98 7.6 TABLE 6 HPLC Analysis HPLC Analysis Wt. of Adduct (Solid) (Effluent filtrate) Adduct THPE BPA PHENOL THPE BPA PHENOL Example (g) wt percent wt percent wt percent wt. percent wt. percent wt. percent 12 8.70 60.59 15.99 23.42 23.42 21.86 54.72 13 12.22 60.61 10.72 28.67 16.73 21.54 61.72 14 10.60 54.47 11.06 34.48 12.56 16.09 71.35 15 6.52 48.83 7.52 43.66 12.03 10.66 77.31 16 6.09 83.20 0.50 16.31 26.81 0.25 72.94 17 9.70 85.46 0.00 14.54 20.21 0.34 79.45 18 21.83 76.62 0.38 23.00 25.15 0.29 74.56 19 2.45 87.97 0.45 11.58 19.61 0.29 80.09 20 2.20 77.82 0.35 21.83 11.93 0.26 87.81 EXAMPLE 21 In this example, THPE was prepared as per given above, and then the catalyst was recycled 10 times. The reactants phenol, PD, 3-MPA were taken along with A-121 2percent CL IER catalyst and heated at 75° C.for 24 hours. This mixture was filtered off to obtain the catalyst and to the filtrate was added 3:1 volume by volume ethylene dichloride based on the total volume of the reaction mixture. The catalyst was then again washed with about 50 ml ethylene dichloride and reused in the next batch. The catalyst was recovered in a similar manner as described above and reused for 9 subsequent batches using the quantity of phenol, PD and 3-MPA provided in Table 7 below. Table 7 also indicates the wt. percent of the THPE and BPA as obtained by HPLC analysis of the reaction mixture. TABLE 7 HPLC analysis Phenol PD 3-MPA IER Catalyst Time in THPE BPA Example in g in g in g in g hours Yield percent yield percent 21 282 15.023 4.77 32.1 24 NA NA 21a 282 15.02 4.77 Recycled from 21 24 33.41 54.25 21b 282 15.02 4.77 Recycled from 21a 24 NA NA 21c 282 15.02 4.77 Recycled from 21b 24 41.38 62.31 21d 282 15.02 4.77 Recycled from 21c 24 NA NA 21e 282 15.02 4.77 Recycled from 21d 24 NA NA 21f 282 15.02 4.77 Recycled from 21e 24 NA NA 21g 282 15.02 4.77 Recycled from 21f 24 24.31 30.09 21h 282 15.02 4.77 Recycled from 21g 24 24.84 28.95 21i 282 15.02 4.77 Recycled from 21h 24 24.47 26.78 NA --> data not available.These examples provide a method for the preparation HPE as generally outlined in Example 1. Examples 2-5 employed 3-MPSA as the talyst whereas Examples 6-7 utilized 3-MPA. The reaction contents, time, and s are included in Table 3 below. All the reactions were carried out at a erature of about 65° C. The weight percent of the co-catalyst and catalyst used is d on the total weight of the reaction mixture, i.e., total weight of phenol and PD. TABLE 3 HPLC analysis results Phenol Co-catalyst IER Resin Time THPE BPA Ex. PD (g) (g) (g) A-121 (g) (hours) yield (percent) yield (percent) 2 4.1 50 0.54 4.33 2 7.43 2.27 3-MPSA 4 0.53 4.27 20 40.91 62.68 22 46.34 67.87 24 45.66 67.15 26 51.96 70.76 46 57.47 71.18 48.5 57.16 71.16 3 4.1 50 1.08 4.89 2 2.08 1.11 3-MPSA 4 0.39 2.05 20 46.24 62.67 22 49.65 64.94 24 48.07 66.19 26 49.30 66.32 28 48.04 65.54 48.5 54.65 67.73 4 4.1 50 1.62 4.89 2 4.19 2.09 3-MPSA 4 14.84 9.88 20 46.22 66.37 26 44.90 64.92 28.5 49.36 66.97 28.5 49.85 67.15 5 2.7 50 0.54 3.20 20 57.60 70.49 3-MPSA 22 56.55 71.09 26 60.79 74.41 44 58.36 74.98 46 58.79 72.86 46 59.00 73.06 6 2.5 47 0.79 4.95 24 49.05 78.15 3-MPA 7 2.5 47 0.79 9.90 18 45.94 80.92 3-MPAIn this example, THPE was purified by forming the adduct. In a 500 ml round bottom flask, THPE (15.37 g), BPA (11.4 g) and phenol (37.64 g) (THPE:BPA:phenol::1:1:8) were taken and heated to about 150° C.in an hour to obtain a homogenous solution. The heating was continued for another 1 hour and then the temperature was decreased at a rate of about 1° C. per minute, when the solids precipitated out at about 126° C. The mixture was then allowed to stand for another 20 minutes and then filtered. The product obtained was analyzed using HPLC and indicated 60.61 weight percent (wt. percent) THPE, 10.71 wt. percent BPA and 28.66 wt. percent phenol.In this example, THPE was prepared using phenol and 2, 4-pentanedione. Phenol (306 g) 2, 4-Pentanedione (PD, 25 g) and 3-mercaptopropionic acid (3-MPA, 4.96 g) were charged to a 1 L 4-necked round bottom flask equipped with overhead stirrer and a nitrogen inlet. To this reaction mixture methanesulfonic acid (MSA, 16.5 g) was added in a drop-wise manner maintaining the temperature below 35 C. After complete addition of MSA, the temperature was raised to 55 C. and stirring was continued for 22 hours. The reaction mixture turned into a thick red slurry. This red slurry was poured into 2 L conical flask and diluted with 1.1 L of ethylene dichloride (EDC) and stirred for 3 hours at room temperature (RT, 24 C.). The solid material that precipitated from this reaction mixture was then filtered and washed with sufficient amount of EDC (approximately 150 ml) till the filtrate obtained was colorless. The buff colored crude solid obtained was dried on rotavac for 3 hours to 4 hours (at 45 C., 50 millibar). The solids were taken in a 1 L round bottom flask and slurried with 150 ml. of methanol:water (20:80 volume by volume) and stirred for half an hour. The solid material obtained was filtered and dried in rotavac under vacuum for 3 hours to 4 hours (at 60 C., 50 millibar). The solids so obtained were then refluxed in 85 ml. of methanol and 50 milligrams (mg) of NaBH4 was added. The color of the solution turned to pale yellow to which 170 ml of demineralized water containing 50 mg of NaBH4 was added. This mixture was then allowed to cool to room temperature and stirred for 2 hours. Solid material precipitated out. This was then filtered and washed with approximately 50 ml cold methanol:water (20:80) till the filtrate obtained colorless. The solid material so obtained was dried on rotavac for 3 hours to 4 hours (at 60 C., 50 millibar) to provide a white colored product with combined THPE and BPA together purity >99.5percent, by HPLC and color test (UV test) in about 52percent yield. The color values were analyzed spectrophotometrically by weighing 2.5 grams of the particular 1, 1, 1-tris(4-hydroxyphenyl)alkane in a 30 milliliters vial and dissolving the sample in 5 grams of methanol. The percentage transmission was then measured using this solution in a UV-visible spectrophotometer in the range of 300 nanometer (nm) to 750 nm ; EXAMPLES 5-11 These examples were carried out in a similar manner as described in Example 4, and the recycle steps were carried out as in Example 1. The results are shown in Table 3 below. Table 3 indicates the transmission values in percentage in the UV visible range for some of the Examples 4-11 in addition to providing the yields obtained in these examples.

Intermediates

Plastic and rubber products not covered elsewhere

100,000 - 500,000 lb

Molecular Weight:306.4
XLogP3:4.1
Hydrogen Bond Donor Count:3
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:306.125594432
Monoisotopic Mass:306.125594432
Topological Polar Surface Area:60.7
Heavy Atom Count:23
Complexity:304
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes