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    Home > Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate
    Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate structure

    Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

    • CAS No:

      6386-38-5

    • Formula:

      C18H28O3

    • Synonyms:

      ralox35;Methyl 3-(3,5-di-ter;METHYL 3,5-DI-TERT-BUTYL-4-HYDROXYHYDROCINNAMATE;METHYL 3,5-DI-TERT-BUTYL-4-HYDROXYPHENYLPROPIONATE;Methyl 3-(3,5-tertbutyl-4-hydroxyphenyl)propionate;METHY(3,5-DI-TERT-BUTYL-4-HYDROXYPHENYL) PROPIONATE;3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester;Methyl 3-(4-hydroxy-3,5-di-t-butylphenyl) propionate;Methyl-3(3,5-di-tert.-butyl-4-hydroxyphenyl)propionat;METHYL 3-(3,5-DI-TERT-BUTYL-4-HYDROXYPHENYL)PROPIONATE

    • China Export:

      From 2018.11 to 2019.11, total export volume of Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate from China was 35,390,099KG while total export value was $168,124,918. The biggest proportion of exporting volume in the last 12 months was 10.21% in 2019.03.

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    Description

    OtherSolid

    Basic Attributes

    • 6386-38-5

    • C18H28O3

    • 292.41

    • 292.203857

    • 46.5

    • 5

    • 228-985-4

    • PXMJCECEFTYEKE-UHFFFAOYSA-N

    • 3

    • 1

    • 0.61

    • 6

    Characteristics

    • OtherSolid

    • 1.0±0.1 g/cm3

    • 60-67°C

    • 124.2±19.3 °C

    • 1.500

    Safety Information

    • IRRITANT

    • 2918290000

    • 36/37/38

    • 26-36/37/39

    • P201, P202, P260, P273, P281, P308+P313, P314, P391, P405, P501

    • H361

    Production Methods

    (1) equipped with N2 air duct, Three rotor, and a dropping funnel was added to the reaction flask 2, 6-di-t-butylphenol, and 20.6g of zinc carbonate mass ratio of 1.5 and a mixture of tributyl tin acetate 0.072g, Melting under nitrogen protection and heating to obtain a reactant; (2) When the reaction temperature reaches 70 ° C, To the reactant of the step (1), 8.24 g of the reactant methyl acrylate was added dropwise.After the completion of the dropwise addition, the reaction was continued for 0.5 hours.After heating to 90 ° C for 1 hour, Cooled to 80 ° C, Adjust the reaction solution to neutral with hydrochloric acid, crystallization, After suction filtration, Get the product;The final product yield was 99percent and the purity without recrystallization was as high as 99.5percent.A 1-liter round bottom Pyrex flask equipped with a magnetic stir bar, temperature probe, heating mantle, and total condenser for distillate removal was used. The flask was initially charged with 350.7 g of molten 2, 6-di-tert-butylphenol (2, 6-DTBP, 1.70 mol) at 40 to 50° C., 2.42 g of potassium hydroxide (KOH) pellet, and 14.7 g of DMSO. The pressure was then reduced to 15 mm Hg and the temperature was increased from 40° C. to 115° C. over 70 minutes to remove the water by-product. The resulting white slurry was then cooled to 110° C. A water-cooled total reflux condenser and a 250-ml addition funnel containing 155.6 g of methyl acrylate were installed to the reactor. The methyl acrylate (MA) was added dropwise over 30 minutes, during which the temperature of the reactor was allowed to rise from 110° C. to 129° C. The reactor was heated further to 135° C. in 6 minutes, then cooled to 110° C. and held at 110° C. for 170 minutes. The red clear solution was analyzed by Gas Chromatography (GC) and found to contain 1.2 area percent 2, 6-di-tert-butylphenol and 96.0 area percent 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester. The pressure was then reduced to 20 mm Hg, and the excess methyl acrylate was stripped at 110° C. The intermediate was analyzed by GC and found to contain 93.9 wt. percent 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester and 0.67 wt. percent 2, 6-DTBP. A 21.5 g portion of the 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester intermediate was used for physical property measurements. This example demonstrates another two-step method for the production of 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester, which is suitable for use as an antioxidant. Step 1: Michael Reaction. A 12-liter round bottom Pyrex flask equipped with an overhead agitator, temperature probe, heating mantle, and a reflux condenser in series of a total condenser for distillate removal were used. The flask was initially charged with 4126.4 g of molten 2, 6-DTBP (20.0 mol) at 40 to 50° C., 28.1 g of KOH pellet (0.50 mol), and 85.9 g of DMSO (1.1 mol). The pressure was then reduced to 20 mm Hg and the temperature was increased from 40° C. to 126° C. over 76 minutes to remove the water by-product. The resulting white slurry was then cooled to 110° C. Cooling water was then put to the jacket of the reflux condenser and 995.2 g of methyl acrylate (11.56 mol) was then added dropwise from a 1000-ml funnel to the reactor over 37 minutes, during which time the reactor temperature was allowed to rise from 110° C. to 117° C. A stream of nitrogen was injected between the heating mantle and the reactor wall to remove the heat. The dropping funnel was immediately recharged with an additional 847.4 g of methyl acrylate (9.84 mol), which was added dropwise to the reactor over 39 minutes, while the reactor temperature was allowed to increase to 130° C. The reactor temperature was then brought to 140° C. over 10 minutes before cooling to 110° C. over 25 minutes. After a 110 minute hold at 110° C., the reaction mass was found to contain 1.58 area percent 2, 6-DTBP and 96.7 area percent 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester. The reaction mass was held for 30 minutes longer at 110° C., before the excess methyl acrylate was stripped off at 110° C. and 20 mm Hg. The resulting 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester was analyzed by GC and found to contain 0.47 wt. percent 2, 6-DTBP and 94.85 wt. percent 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, and 1.75 area percent diesters.A 1-liter round bottom Pyrex flask equipped with a magnetic stir bar, thermal probe, heating mantle, water-cooled total reflux condenser, and 250-ml addition funnel were used. The flask was initially charged with 309.3 g of molten 2, 6-DTBP (1.50 mol) at 40-50° C., 4.21 g of potassium tert-butoxide (t-BuOK), and 16.82 g of tetrahydrofuran (THF) to form a slurry. The slurry was heated to 110° C. and 142.0 g of methyl acrylate was added dropwise from the addition funnel over 98 minutes while the reactor was maintained at 110-120° C. After holding at 120° C. for 3.6 additional hours, the red clear reaction mass was found (by GC) to contain 0.46 area percent 2, 6-DTBP and 98.5 area percent 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester. The pressure was then reduced to 20 mm Hg to strip off the THF and excess methyl acrylate. The methyl ester intermediate contained 96.3 wt. percent 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, 0.11 wt. percent 2, 6-DTBP, 0.04 wt percent methyl acrylate, and 0.38 wt. percent THF.General procedure: According to a literature protocol.[1] Propanoic acid derivative (10 g) was dissolved inmethanol (80 ml) and H2SO4 (700μl, 6 mmol) added. The resulting solution was refluxed for16 h and then allowed to cool to room temperature. The reaction mixture was reduced todryness and re-dissolved in ethyl acetate (20 ml). The organic phase was washed withsaturated aqueous sodium hydrogen carbonate (10 ml), brine (10 ml) and dried over MgSO4.Removal of the solvent gave the desired methyl ester. (Note: column chromatography is oftennot required for the methyl ester starting materials).into a 500 ml reactor equipped with a stirrer, a thermometer, a nitrogen gas pipe, a condenser, a trap and a pressure reducing device were added 146.2 g (0.50 mol) Methyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate and 130.2g(1.00mol) isopropyl alcohol , then followed by addition of 1.5 g (0.0051 mol) of Tetraisopropyl titanate, close the apparatus and nitrogen was evacuated. Gradually heated to 160-170 C, then slowly reduced to 50mmHg and 6 hours of reaction to collect methanol 16.0g. After cooling to 40 C, 0.62 g (0.0069 mmol) of ethanedioic acid (oxalic acid) was added and the after mixture was stirred at 40 C for 20 minutes the filtration was carried out . The temperature was raised to 160-170 C and the excess isooctanol was recovered by distillation under reduced pressure to a <5 mm Hg to give 194.0 g of a colorless transparent product , yield of 99.41%. purity 99.45%.A Vigreux column equipped with an air-cooled partial condenser and a -15 C. glycol-cooled total condenser was installed to the reactor. The remaining 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester intermediate (1.63 mol) was added with 225.8 g of isooctanol. The mixture was heated slowly from 65 C. to 176 C. over 3.2 hours at a reduced pressure of 300 mm Hg initially to 60 mm Hg at end, during which approximately 65 ml of methanol distillate was collected in the trap receiver. The resulting reaction mass was found (by GC) to contain 2.7 area % isooctanol, 0.83 area % 2, 6-DTBP, 0.81 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, and 94.8 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester. After removing the column and the air-cooled partial condenser, the excess isooctanol was stripped off at 5 mm Hg and 185 C. The resulting 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester crude product was found (by GC) to contain 0.35 area % isooctanol, 0.30 area % 2, 6-DTBP, 0.68 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, and 97.34 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester. Step 2: Transesterification Reaction. The above-mentioned reflux condenser was packed with 4.5 S.S. Propak, which improved the separation of MeOH from the isooctanol and DMSO. The 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester intermediate was added with 2, 789.6 g of Isooctanol (21.42 mol). The mixture was heated slowly from 71 C. to 166 C. over 4.2 hours at 25 mm Hg, during which 661 g of methanol was collected in the trap receiver. After removing the reflux condenser, the excess isooctanol and DMSO (206.3 g collected) were stripped off at 5 mm Hg and 185 C.A Vigreux column equipped with a water-cooled air-cooled partial condenser and a -15 C. glycol-cooled total condenser was installed to the reactor. The above methyl ester intermediate was added with 200.4 g of Exxal-8 isooctanol (1.539 mol). The mixture was heated slowly from 43 C. to 155 C. at reduced pressure of 300 down to 50 mm Hg over 82 minutes. Approximately 55 ml of methanol distillate was collected. Then 6 ml of toluene was added dropwise over 50 minutes to the reactor, which was kept at 155 C. and 25-50 mm Hg. The toluene was used as a chaser to strip off the methanol byproduct from the reaction mass to drive the reaction to completion. At the end of the toluene feed, the reaction mass was found (by GC) containing 1.8 area % isooctanol, 0.19 area % 2, 6-DTBP, 4.89 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, and 92.3 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester, indicating incompletion of the reaction of methyl ester to isooctyl ester. An additional 11.1 g of Exxal-8 isooctanol (0.085 mol) was charged to the reactor. Then 17 ml of toluene was added dropwise over 83 minutes, while keeping the reactor at 155 C. and 30 mm Hg. The resulting product was analyzed by GC and found to contain 1.65 area % isooctanol, 0.15 area % 2, 6-DTBP, 1.12 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, and 96.6 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester. After removing the column and the air-cooled partial condenser, an additional 25 ml of toluene was added as a chaser to strip off the excess isooctanol at 20 mm Hg and 150-155 C. The resulting product was found (by GC) to contain 1.3 area % isooctanol, 0.2 area % 2, 6-DTBP, 1.08 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, and 97.1 area % 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid, isooctyl ester.584 g of methyl beta-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate, 541 g octadecanol, 0.58gSodium montmorillonite, 100 ml of methanol was added to the flask with mechanical stirring, Thermometer socket, In a 2000 ml four-necked flask equipped with a stirrer, Heating the material with a heating jacket, And stirring is started, Temperature reached 110-120 , Filled with nitrogen, So that the reaction system pressure control in 2-3MPa, 7h after the end of the reaction, Cooled to 20 C, filter, drying, octadecanol beta-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate.(1) A reaction product of methyl 5-(3, 5-di-tert-butyl-4-hydroxyphenyl)propanoate 5.256 g and a reaction mixture were placed in a three-necked flask.200 mL of a mixed solution of ethylene glycol and toluene (V ethylene glycol: V toluene = 1:50), After joining the rotor, And fix the reflux condenser to the three-necked flask.Vacuum treatment under nitrogen protection, Cycle 3 times;(2) The vacuum-treated three-necked flask containing the reactant obtained in the step (1) is subjected to an ice bath for 20 minutes to obtain a reaction liquid;(3) adding 0.00657 g of tetrabutyl titanate and tetramethyl titanate in a mass ratio of 1:1 to the reaction liquid of the step (2).After one hour of reaction, Adding the reactant stearyl alcohol 4.05g, Further adding 0.00657 g of tetrabutyl titanate and tetrabutyl zirconate at a mass ratio of 1:1.Remove the ice bath, Place the three-necked flask containing the reaction solution in an oil bath.After reacting at 80 C for 3 hours, It was cooled to 60 C, crystallized, and suction filtered to give a product.The synthesis of methyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propanoate is shown in Example 1.The final product yield was 99.6% and the purity was as high as 99.8%.EXAMPLE 6 To a reaction vessel equipped with a condenser, a thermometer, a trap, a nitrogen sparge tube and a mechanical stirrer are added 307 g (5 mole % excess) methyl 3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 270.5 g commercial stearyl alcohol and 10 wt % of N-methylpyrrolidinone (NMP). Then 2 mole % of lithium amide is added with agitation and the reaction mixture is heated to 115-155 C. at atmospheric pressure while continuously sparging with nitrogen gas at a rate of 0.5 L/min. for 1.5 hours. Analysis by gas chromatography indicated that 99.9% of octadecyl 3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionate is obtained.EXAMPLE 3 Octadecyl 3, 5-Di-tert-butyl-4-hydroxyhydrocinnamate The general procedure of is repeated, but using 337.0 g (1.246 mole) of octadecyl alcohol and 391.9 g (1.340 mole) of methyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate and a reflux temperature of between 189 and 201 C. After 2.5 hours, analysis of the contents of the reaction flask using Gas shows a mixture of 32.1 wt % of the title compound, 32.0 wt % of methyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate and 29.6 wt % octadecyl alcohol.EXAMPLE 5 Octadecyl 3, 5-Di-tert-butyl-4-hydroxyhydrocinnamate The general procedure of is repeated, but using 382.9 g (1.416 mole) of octadecyl alcohol and 471.3 g (1.612 mole) of methyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate and employing 2 ounces (30.1 g) of PROPAK and 2.5 ounces (69.4 g) of TiS catalyst. The system is brought to reflux at a pressure of 6-8 mm Hg and a temperature of between 190 and 202 C. After 2.5 hours, analysis of the contents of the reaction flask using Gas Chromatography shows a mixture of 51.7 wt % of the title compound, 26.2 wt % of methyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate and 20.8 wt % octadecyl alcohol.EXAMPLE 1306 g of methyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate (corresponding to 1.05 mole) and 270 g of 1-Octadecanol (corresponding to 1 mole) are used as reactants and put into the reactor, heated to 180 C. till melted, and well stirred. The decompression pump is actuated to reduce the pressure in the reactor down to 80 millibars. Samples of the reactants are taken each 30 minutes and water contents therein are analyzed. When the water content comes to 100 ppm or below, drying of the reactants is finished. Then the decompression pump is turned off and nitrogen gas is introduced into the reactor to return the pressure to the atmospheric pressure. Afterward, the reactor is opened to the atmosphere. Nitrogen gas is introduced into the reactor through the nitrogen-gas emitting belts at the speed of 1 Liter/minute (based on the volume at 25 C. and 1 atm) so as to prevent water and oxygen from entering the reactants.The catalyst solution filtered by the filter plate of the filter pore diameter of 1 mum is taken as the catalyst. The total amount of the catalyst (lithium methoxide) used is 60 ppm based on the amount of the reactants. A syringe is used to preciously take 0.3456 g of the catalyst solution (concentration 10 wt %) and the catalyst solution is divided into two batches for adding to the reactants, respectively.When half of the catalyst is added, transesterification reaction between the reactants is started. After 30 minutes, the remaining half of the catalyst is added into the reactants. Vaporization for removing the methanol by-products from the reactor is continuously performed. After 30 more minutes, (entering the second hour), introduction of nitrogen gas is stopped and decompression evaporation is performed to make the pressure from 1013.25 millibars (the atmospheric pressure) gradually reduce to millibars with a speed of 30 millibars/minutes. Afterward, the pressure is held at 10 millibars until the transesterification reaction is completed. The transesterification reaction takes 5 hours to termination when the decompression pump is turned off and nitrogen gas is introduced to the reactor again to return the pressure to the atmospheric pressure. Afterward, the reactor is opened to the atmosphere. Nitrogen gas is introduced into the reactor through the nitrogen-gas emitting belts at the speed of 1 Liter/minute (based on the volume at 25 C. and 1 atm). Samples are then taken for analysis of the conversion rate and color of the crude product of Octadecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate. The results of analysis are shown in Table 1.The crude product of Octadecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate is then cooled to 40 C. Then 2000 g of ethanol is put into the reactor which is then heated to 45 C. till the crude product is melted. For crystallization, the temperature of the crude product is reduced to 20 C. at a speed of 0.5 C./minute so as to precipitate crystals. The crystals are then collected by filtering and dried by fluidized bed drying and heated air of 45 C. so as to remove ethanol solvent therefrom. After drying, samples are collected for analysis to measure the purity and APHA color value of the product of Octadecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate. The readings are shown in Table 1.

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    Material and Products

    China Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Export Data

    Data referenced from General Administration of Customs,P.R.China

    2018.11-2019.11 China - America  Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Export Data

    From 2018.11 to 2019.11, total export volume of Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate from China to America was 3,664,468KG while total export value was $19,818,392. The biggest proportion of exporting volume in the last 12 months was 16.56% in 2019.05.

    2018.11-2019.11 China Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Export Data

    From 2018.11 to 2019.11, total export volume of Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate from China was 35,390,099KG while total export value was $168,124,918. The biggest proportion of exporting volume in the last 12 months was 10.21% in 2019.03.

    2018.11-2019.11 TOP10 Purchasing Countries' Export Data of Chinese Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

    From 2018.11 to 2019.11, China has exported Methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate to 98 countries in total. Country ranks by import volume from high to low is India, Japan, America, Korea, Taiwan, Singapore, Belgium, Saudi Arabia, Netherlands, Thailand. The highest export volume was China to India, accounting for 13.63% of the total volume of China.

    Check Export Data for More Purchasing Countries

    Purchasing Country Export Volume(KG) Export Percentage Export Value($)

    India

    9,436,853

    13.63%

    35,952,609

    Japan

    6,889,463

    9.95%

    40,115,697

    America

    3,664,468

    5.29%

    19,818,392

    Korea

    2,853,476

    4.12%

    11,237,896

    Taiwan

    1,773,214

    2.56%

    8,015,104

    Singapore

    1,545,135

    2.23%

    6,371,111

    Belgium

    1,313,233

    1.90%

    5,793,401

    Saudi Arabia

    873,215

    1.26%

    3,229,255

    Netherlands

    808,504

    1.17%

    4,189,099

    Thailand

    753,943

    1.09%

    3,283,009

    Israel

    666,250

    0.96%

    2,651,581

    Malaysia

    618,065

    0.89%

    2,685,498

    Iran

    602,745

    0.87%

    2,557,657

    Germany

    420,011

    0.61%

    3,102,146

    Spain

    375,432

    0.54%

    4,690,433

    United Arab Emirates

    364,075

    0.53%

    1,365,977

    Italy

    340,541

    0.49%

    1,631,095

    Brazil

    257,289

    0.37%

    1,217,411

    Indonesia

    221,474

    0.32%

    977,188

    Russia

    127,237

    0.18%

    573,119

    Turkey

    120,164

    0.17%

    502,966

    Pakistan

    106,230

    0.15%

    421,829

    Argentina

    104,370

    0.15%

    466,182

    Vietnam

    104,010

    0.15%

    431,148

    Mexico

    95,341

    0.14%

    692,209

    Ireland

    92,000

    0.13%

    353,685

    Colombia

    81,041

    0.12%

    514,722

    United Kingdom

    73,599

    0.11%

    1,185,955

    Brunei

    73,000

    0.11%

    268,075

    Canada

    59,065

    0.09%

    240,441

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