* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Stage #1: Inert atmosphere; Heating Stage #2: at 70 - 90℃; for 1.5 h; Inert atmosphere
(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.
96 - 96.7 %Chromat.
Stage #1: at 40 - 50℃; Stage #2: at 110 - 140℃; for 1.85 - 3.43333 h;
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. EXAMPLE 2 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.
98.5 %Chromat.
Stage #1: at 40 - 110℃; Stage #2: at 110 - 120℃; for 5.23333 h;
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.
Reference：
[1] Patent: CN108358781, 2018, A, . Location in patent: Paragraph 0046-0049
[2] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1989, vol. 38, # 8.2, p. 1677 - 1682[3] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1989, # 8, p. 1829 - 1835
[4] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1989, vol. 38, # 8.2, p. 1677 - 1682[5] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1989, # 8, p. 1829 - 1835
[6] Russian Chemical Bulletin, 2007, vol. 56, # 10, p. 2038 - 2042
[7] Patent: US2005/192455, 2005, A1, . Location in patent: Page/Page column 14
[8] Patent: US2005/192455, 2005, A1, . Location in patent: Page/Page column 11-12
[9] Patent: US2005/192455, 2005, A1, . Location in patent: Page/Page column 14-15
2
[ 67-56-1 ]
[ 20170-32-5 ]
[ 6386-38-5 ]
Yield
Reaction Conditions
Operation in experiment
90%
for 16 h; Reflux
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).
Reference：
[1] Tetrahedron Letters, 2013, vol. 54, # 25, p. 3294 - 3297
[2] Russian Chemical Bulletin, 2007, vol. 56, # 6, p. 1119 - 1124
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1984, vol. 20, p. 1732 - 1737[2] Zhurnal Organicheskoi Khimii, 1984, vol. 20, # 9, p. 1899 - 1905
11
[ 128-39-2 ]
[ 292638-85-8 ]
[ 118-82-1 ]
[ 128-38-1 ]
[ 80099-80-5 ]
[ 95683-83-3 ]
[ 6386-38-5 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1984, vol. 20, p. 1732 - 1737[2] Zhurnal Organicheskoi Khimii, 1984, vol. 20, # 9, p. 1899 - 1905
12
[ 55894-67-2 ]
[ 292638-85-8 ]
[ 6386-38-5 ]
Reference：
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1983, vol. 32, # 1, p. 59 - 62[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1983, # 1, p. 71 - 75
13
[ 128-39-2 ]
[ 7175-96-4 ]
[ 6386-38-5 ]
Reference：
[1] Russian Chemical Bulletin, 2002, vol. 51, # 12, p. 2189 - 2195
14
[ 128-39-2 ]
[ 52977-87-4 ]
[ 6386-38-5 ]
Reference：
[1] Russian Chemical Bulletin, 2002, vol. 51, # 12, p. 2189 - 2195
15
[ 128-39-2 ]
[ 7175-96-4 ]
[ 6386-38-5 ]
Reference：
[1] Russian Chemical Bulletin, 2002, vol. 51, # 12, p. 2189 - 2195
16
[ 128-39-2 ]
[ 292638-85-8 ]
[ 128-37-0 ]
[ 86860-74-4 ]
[ 6386-38-5 ]
Reference：
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1991, vol. 40, # 5.1, p. 877 - 883[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1991, # 5, p. 989 - 996
17
[ 128-39-2 ]
[ 292638-85-8 ]
[ 2455-14-3 ]
[ 6386-38-5 ]
Reference：
[1] Journal of Chemical Research, Synopses, 1995, # 9, p. 366 - 367
[2] Journal of Chemical Research, Synopses, 1995, # 9, p. 366 - 367
18
[ 57559-03-2 ]
[ 59584-42-8 ]
[ 6386-38-5 ]
Reference：
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1985, vol. 34, p. 1833 - 1841[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1985, # 9, p. 1987 - 1996
19
[ 115-77-5 ]
[ 6386-38-5 ]
[ 6683-19-8 ]
Yield
Reaction Conditions
Operation in experiment
98%
With sodium montmorillonite In methanol at 130 - 140℃; for 7 h; Inert atmosphere
The 584gβ- (3,5- di-t-butyl-4-hydroxyphenyl) propionate,68 g of pentaerythritol,0.58 g of sodium montmorillonite,50 ml of methanol was added to the flask with mechanical stirring,Thermometer socket,In a 1000 ml four-necked flask equipped with a stirrer,Heating the material with a heating jacket,And stirring is started,The temperature reaches 130-140 ,Filled with nitrogen,The reaction system pressure was controlled at 3-4 MPa,7h after the end of the reaction,Cooling to 25 ,filter,drying,Pentaerythritol tetrakis [β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. The results of liquid chromatography, the results shown in Figure 1,The absorption peak at the retention time of 2.643 min belongs to 3.5 methyl ester with the content of 0.43percent.The absorption peak at the retention time of 3.29 min is attributed toPentaerythritol tris [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], content of 0.69percent;The absorption peak at 3.84 min was assigned to dealkylationPentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] in 0.55percent;The absorption peak at the retention time of 4.747 min is attributed toPentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] in 96.45percentTherefore, the synthesis of pentaerythritol tetrakis [[beta] - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] in the present method meets the industry standard of not less than 94percent. The yield of the product was 98percent.
96.7%
at 185℃; for 7 h;
Take pentaerythritol 6.8g, 3,5-methyl ester 65.8g and ionic liquid catalyst [Bmim] OH 0.34g added to fourBottle, the reaction pressure is -0.1MPa, reaction at 185 7h, after the reaction is hot (70 or so) was added 90ml solvent was allowed to standStratification, the upper organic phase, the lower ionic liquid phase, ionic liquid recycling recycling, organic phase recrystallization to give the productAntioxidant 1010. HPLC showed that the target product pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4- hydroxyphenyl) propionate]The amount can reach 98.6percent, yield 96.7percent.
Reference：
[1] Patent: CN107011149, 2017, A, . Location in patent: Paragraph 0064-0067
25
[ 6386-38-5 ]
[ 5597-50-2 ]
[ 36837-50-0 ]
[ 115-11-7 ]
Reference：
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1987, vol. 36, # 4, p. 681 - 684[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1987, # 4, p. 752 - 756
26
[ 6386-38-5 ]
[ 20170-32-5 ]
Yield
Reaction Conditions
Operation in experiment
115 g
With sodium hydroxide In methanol; water for 2 h; Heating; Inert atmosphere
In a nitrogen atmosphere,117 g (0.4 mol) of methyl β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionateAnd anhydrous methanol 126.6g added to the reactor, heated to boiling,120 mL of a 30percent by weight NaOH aqueous solution was added and kept for 2 h, then 80 mL of a 10 wtpercent HCl solution was added, stirred and cooled to room temperature, filtered, washed with deionized water until neutral,The filter cake was dried at 110 ° C for 4 h to give 115 g of white solid A1.
Reference：
[1] Patent: US4713475, 1987, A,
[2] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1982, vol. 31, # 7, p. 1417 - 1420[3] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1982, # 7, p. 1594 - 1597
[4] Patent: CN104211616, 2016, B, . Location in patent: Paragraph 0064-0066
27
[ 6386-38-5 ]
[ 23128-74-7 ]
Reference：
[1] Patent: CN104211616, 2016, B,
28
[ 6386-38-5 ]
[ 82304-66-3 ]
Reference：
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1982, vol. 31, # 7, p. 1417 - 1420[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1982, # 7, p. 1594 - 1597
[3] Tetrahedron Letters, 2013, vol. 54, # 25, p. 3294 - 3297
29
[ 67-56-1 ]
[ 6386-38-5 ]
[ 719-22-2 ]
[ 82304-66-3 ]
[ 131692-75-6 ]
Reference：
[1] J. Appl. Chem. USSR (Engl. Transl.), 1990, vol. 63, # 8.1, p. 1625 - 1629[2] Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1990, vol. 63, # 8, p. 1761 - 1765
30
[ 6386-38-5 ]
[ 719-22-2 ]
[ 82304-66-3 ]
[ 131692-75-6 ]
Reference：
[1] J. Appl. Chem. USSR (Engl. Transl.), 1990, vol. 63, # 8.1, p. 1625 - 1629[2] Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1990, vol. 63, # 8, p. 1761 - 1765
Reference：
[1] Patent: CN107011149, 2017, A, . Location in patent: Paragraph 0064-0067
35
[ 6386-38-5 ]
[ 5597-50-2 ]
[ 36837-50-0 ]
[ 115-11-7 ]
Reference：
[1] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1987, vol. 36, # 4, p. 681 - 684[2] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1987, # 4, p. 752 - 756
(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 99% and the purity without recrystallization was as high as 99.5%.
With dimethyl sulfoxide;potassium hydroxide; at 120℃; for 3.75h;Product distribution / selectivity;
Step 1: Preparation of 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester Into a 1-liter round bottom flask equipped with magnetic stirring bar and connected to a Dean-Stark trap and cooling condenser under N2 atmosphere, the following were charged: 206.3 g 2,6-DTBP (1.00 mol) 31.6 g toluene 1.33 g KOH pellets (23.7 mmol, 2.37 mol %) 4.71 g (-4 mL) DMSO promoter (60 mmol, 6.0 mol %) The reaction was heated to 140 C. to remove the water/toluene azeotrope. A white slurry was obtained and 7.2 g hazy toluene was collected in the trap. The Dean-Stark trap was removed and a cooling condenser was connected to the reactor. The heating was reset to 120 C. Vigorous condensation was observed and 99.1 g (1.15 mol) of methyl acrylate was added over a 45-minute period. After three hours of heating at 120 C., the 2,6-di-tert-butylphenol conversion was about 98.5% complete.
96 - 96.7%Chromat.
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 % 2,6-di-tert-butylphenol and 96.0 area % 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. % 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester and 0.67 wt. % 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. EXAMPLE 2 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 % 2,6-DTBP and 96.7 area % 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. % 2,6-DTBP and 94.85 wt. % 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, and 1.75 area % diesters.
98.5%Chromat.
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 % 2,6-DTBP and 98.5 area % 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. % 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, 0.11 wt. % 2,6-DTBP, 0.04 wt % methyl acrylate, and 0.38 wt. % THF.
bis<2,6-di-t-butyl-4-(2-(methoxycarbonyl)ethyl)phenoxy>dimethylsilane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
22.4 g (46%)
In tetraethylene glycol dimethylether; diethyl ether; water;
EXAMPLE 7 Dimethyl-bis{2,6-di-tert-butyl-4-[2-(methoxycarbonyl)ethyl] -phenoxy}-silane To a stirred suspension of 3.06 grams of sodium hydride in 25 ml of tetraethylene glycol dimethylether is added dropwise a solution of methyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propanoate in 115 ml of tetraethylene glycol dimethylether. The reaction mixture is stirred until hydrogen evolution is complete and then to the resultant reaction mixture is added sequentially 1.65 g of 15-crown-5 and 4.84 g of dichlorodimethylsilane. The reaction mixture is heated at 70 C. for 26 hours and then the cooled reaction mixture is partitioned between 1 liter of diethyl ether and 1 liter of water. The organic phase is separated and then extracted three times with water. The organic phase is dried over anhydrous sodium sulfate and the residue is recrystallized from acetonitrile to give 22.4 g (46%) of a white solid, mp 122-129 C., of the following formula STR13 Analysis: Calculated for C38 H60 O6 Si: C 71.2%; H 9.44%; Found: C 72.5%; H 9.3%.
phenolic monoesters; phenolic diester of thiodiethanol; phenolic monoesters of thiodiethanol; phenolic methyl esters; mixture of[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With lithium methanolate; In methanol; at 170 - 180℃; for 6h;
6.02 g (0.016 mol) lithium methylate (10% in methanol) are added to a mixture of 182. 22 g (0.623 mol) 3- (3, 5-DI-T-BUTYL-4-HYDROXYPHENYL) propionic acid methyl ester, 143.62 g (0.574 mol) 3- (3-T-BUTYL-4-HYDROXY-5-METHYLPHENYL) propionic acid methyl ester, 77.75 g (0.597 mol) ISO-OCTANOL (EXXAL&COMMAT;8) and 39.59 g (0.324 mol) thiodiethylene glycol. The mix- ture is stirred for 6 h at 170-180C under reduced pressure. After cooling to room tempera- ture the raw product is dissolved in 300 mi petroleum ether (b. p. 60-90C), neutralised with some aqueous citric acid and washed with water. After evaporating the solvent under re- duced pressure and drying to constant weight in vacuo a yellowish oil is obtained.
lithium hydroxide; zinc(II) octanoate; at 175℃; for 3 - 27h;Product distribution / selectivity;
PP Base (277g, 15% excess), pentaerythritol (28g) and lithium hydroxide monohydrate (0. 15g, 1. 7mol%/Penta) were charged to 500ml litre 4-necked flask equipped with a stirrer, thermometer, pump inlet and distillation head fitted to a condenser, which in turn goes to a liquid-liquid exchanger containing water and cyclohexane. A pump is used to circulate the cyclohexane from the exchanger back into the reactor at a rate of about 0.4g cyclohexane/PP Base g per hour, thus allowing continual distillation of cyclohexane + by-product methanol (the latter being extracted into water by the exchanger). The reaction mass was heated to 175C with distillation of cyclohexane and methanol. Two shots of zinc octanoate (0.448g, 0. 6mol%/Penta) were added after 5 and 12h. Samples were taken at regular intervals and analysed by HPLC, with results given in area% in the Table below. Time (hrs) PP Acid Disub Tris Anox 20 PP Base 3 0. 4 7. 9 31. 2 27. 3 32. 7 5 0. 4 5. 0 27. 5 38. 6 28. 0 7 0. 4 1. 9 19. 7 56. 2 21. 5 9 0. 4 0. 9 13. 1 66. 8 18. 4 12oui0. 6 7. 8 74. 2 16. 1 14 0_5 03 4. 9 78. 8 15. 0 16 0_5 0. 3 3. 7 80. 2 14. 7 After purification (dilution with cyclohexane, washing, separation of the aqueous layer, drying and crystallisation from cyclohexane), the colour of the Anox 20 final product was found to be APHA 6. Example la Example 1 was repeated but with a reduced excess of PP Base (260g, 8% excess), and with just one shot of zinc octanoate (0.9g, 1. 2mol%/Penta) after 5h. The results are provided in the Table below. Time (hrs) PP Acid Disub Tris Anox 20 PP Base 3 0.4 5.8 29.5 39.4 24.0 5 0. 4 4. 7 27. 2 45. 4 21. 5 7 0.4 2. 2 22. 0 56. 8 17. 6 9 0.4 1. 4 16. 9 65. 1 15. 5 12 0. 5 0. 8 11. 7 73. 5 12. 7 14 0. 6 0. 5 8. 5 77. 9 11. 6 19 0. 7 0. 3 5 80. 0 10. 9 After purification, the colour of the Anox 20 final product was found to be APHA 5 Comparative Example 1 Example 1 was repeated but with lithium hydroxide monohydrate (0.44g, 5mol%/Penta) dosed in eight 0. 055g shots at 2h intervals. The time taken to reach a level of 5% Tris (the point at which the reaction is regarded as complete, and ready to go into the purification stage) was found to be 21h. After purification, the colour of the Anox 20 final product was found to be APHA 14 Comparative Example la Comparative Example 1 was repeated but with lithium hydroxide monohydrate (0.44g, 5mol%/Penta) added all at the beginning of the reaction. The time taken to reach a level of 5% Tris was found to be 28h. After purification, the colour of the Anox 20 final product was found to be APHA 20 Comparative Example lb Comparative example lwas repeated but with lithium hydroxide monohydrate (0. 15g, 1.7 mol%/Penta) and zinc octanoate (0.9g, 1. 2mol%/Penta) added together at the start. The time taken to reach a level of 5% Tris was found to be 27h. After purification, the colour of the Anox 20 final product was found to be APHA 16 These results are summarised in the following Table to illustrate the benefits of the inventive catalyst system
zinc diacetate; lithium acetate; at 180℃; for 1 - 23.5h;Product distribution / selectivity;
PP Base (247g, 15% excess), pentaerythritol (25g) and lithium acetate (0.75g, 3mol%/PE) were charged to 500ml litre 4-necked flask equipped with a stirrer, thermometer, pump inlet and distillation head fitted to a condenser, which in turn goes to a liquid-liquid exchanger containing water and cyclohexane. A pump is used to circulate the cyclohexane from the exchanger back into the reactor at a rate of about 1.6g/min, thus allowing continual distillation of cyclohexane + by-product methanol (the latter being extracted into water by the exchanger). The reaction mass was heated to 180C with distillation of cyclohexane and methanol. Samples were taken at regular intervals and analysed by HPLC, with results given in area % in the Table below. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 2 0. 37 10. 29 29. 95 0. 09 16. 36 40.86 4 0.39 5. 2 28. 38 0. 2 32. 67 31.54 6 0. 41 2. 83 23. 81 0. 41 44. 49 26.43 23 0. 44 0. 33 9. 54 0. 66 68. 83 18.34 47 0. 47 0. 08 4. 98 0. 92 75. 39 16.02 Comparative Example 3 As Comparative Example 2, but instead zinc octanoate (2.9g, 3mol%/PE) was used as catalyst with the following results. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 02 4. 10 0. 62 0. 00 0. 17 89.61 2 0. 00 10. 77 3. 36 0. 01 0. 15 77.15 3 0. 00 15. 63 7. 05 0. 02 0. 40 68. 47 4 0. 00 18. 25 11. 95 0. 01 0. 88 62.05 5 0. 00 18. 28 16. 29 0. 02 1. 52 58. 33 22. 8 0. 00 3. 90 30. 64 0. 71 28. 69 33.22 Example 2 As Comparative Example 2, but with lithium acetate (0.75g, 3mol%/PE) added at the beginning, and zinc acetate (1.43g, 3mol%/PE) added after 4h at 180C, with the following results. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 28 16. 88 18. 49 0. 04 3. 39 55.53 2 0. 40 10. 44 30. 22 0. 40 15. 32 40.53 3 0. 47 6. 96 30.02 0. 55 24. 96 34.75 4 0. 47 5. 34 28.65 0. 63 30. 51 32.08 5 0. 55 2. 92 24. 74 0. 77 40. 26 28.03 6 0. 66 1. 83 20. 54 0.87 47. 36 25.65 22. 3 02. 21 0.02 2. 07 1. 29 74. 53 15.27 Example 3 As Example 2, but with a reduced amount of PP Base (227.4g, 8% excess) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 30 17. 88 21. 13 0. 05 4. 42 50. 82 2 0.41 12. 02 31. 63 0. 41 15. 92 36.66 3 0.60 6. 72 29. 12 0. 75 33. 28 27.04 4 0. 67 6. 44 29. 06 0. 84 36. 25 26.24 5 0.81 3. 48 26. 25 0. 94 43. 25 22.47 6 0. 89 2. 36 22. 82 1. 09 49. 23 20. 30 7 1. 06 1. 61 19. 69 1. 22 55. 20 17.47 23. 3 2. 78 0. 08 4. 58 1. 67 76. 42 8. 86 Example 4 As Example 2, but with a lower amount of zinc acetate (0.72g, 1. 5mol%/PE) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 24 15. 87 22. 86 0. 07 5. 41 51.39 2 0.37 9. 59 30. 26 0. 41 17. 29 39.67 3 0.40 6.75 29.66 0.51 25. 16 35. 31 4 0.38 5. 15 28. 12 0.58 30. 92 32.63 5 0.52 3.18 24.96 0.69 39.20 28.99 6 0.61 1.90 20.72 0.80 46. 75 26.54 23.3 1.64 0.02 2.47 1.23 74. 42 15.68 Example 5 As Example 4, but with a lower amount of lithium acetate (0.38g, 1. 5mol%/PE) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1OH16. 39 14. 710032. 32 60.52 2 0. 14 12. 51 28. 61 0. 13 11. 81 43.90 3 0. 21 9. 02 30. 41 0. 24 19. 56 38.24 4 0. 23 6. 94 29. 83 0. 47 25. 34 35.01 50294. 48 28. 2105632. 66 31.46 6 0.30 2.97 25.29 0.66 40.88 27.33 22.5 1.03 0.01 1.84 1.16 75. 42 16.66
zinc(II) acetylacetonate; lithium acetate; for 4 - 10h;Product distribution / selectivity;
As Example 2, but with lithium acetate (0.2g, 1. 5mol%/l ? P base) added at the beginning and zinc acetylacetonate (0.73g, 1. 5mol%/PP base) added after 4h, with the following results obtained. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 3 0. 3 5. 0 27. 0 0. 6 28. 7 35. 8 4 0. 3 2. 9 23. 4 0. 7 39. 3 31. 0 6 0. 4 0. 5 10. 9 1. 0 61. 7 20. 9 10 0. 4 0 1. 4 1. 1 75. 1 18.
lithium hydroxide; zinc(II) octanoate; at 175℃; for 3 - 27h;Product distribution / selectivity;
PP Base (277g, 15% excess), pentaerythritol (28g) and lithium hydroxide monohydrate (0. 15g, 1. 7mol%/Penta) were charged to 500ml litre 4-necked flask equipped with a stirrer, thermometer, pump inlet and distillation head fitted to a condenser, which in turn goes to a liquid-liquid exchanger containing water and cyclohexane. A pump is used to circulate the cyclohexane from the exchanger back into the reactor at a rate of about 0.4g cyclohexane/PP Base g per hour, thus allowing continual distillation of cyclohexane + by-product methanol (the latter being extracted into water by the exchanger). The reaction mass was heated to 175C with distillation of cyclohexane and methanol. Two shots of zinc octanoate (0.448g, 0. 6mol%/Penta) were added after 5 and 12h. Samples were taken at regular intervals and analysed by HPLC, with results given in area% in the Table below. Time (hrs) PP Acid Disub Tris Anox 20 PP Base 3 0. 4 7. 9 31. 2 27. 3 32. 7 5 0. 4 5. 0 27. 5 38. 6 28. 0 7 0. 4 1. 9 19. 7 56. 2 21. 5 9 0. 4 0. 9 13. 1 66. 8 18. 4 12oui0. 6 7. 8 74. 2 16. 1 14 0_5 03 4. 9 78. 8 15. 0 16 0_5 0. 3 3. 7 80. 2 14. 7 After purification (dilution with cyclohexane, washing, separation of the aqueous layer, drying and crystallisation from cyclohexane), the colour of the Anox 20 final product was found to be APHA 6. Example la Example 1 was repeated but with a reduced excess of PP Base (260g, 8% excess), and with just one shot of zinc octanoate (0.9g, 1. 2mol%/Penta) after 5h. The results are provided in the Table below. Time (hrs) PP Acid Disub Tris Anox 20 PP Base 3 0.4 5.8 29.5 39.4 24.0 5 0. 4 4. 7 27. 2 45. 4 21. 5 7 0.4 2. 2 22. 0 56. 8 17. 6 9 0.4 1. 4 16. 9 65. 1 15. 5 12 0. 5 0. 8 11. 7 73. 5 12. 7 14 0. 6 0. 5 8. 5 77. 9 11. 6 19 0. 7 0. 3 5 80. 0 10. 9 After purification, the colour of the Anox 20 final product was found to be APHA 5 Comparative Example 1 Example 1 was repeated but with lithium hydroxide monohydrate (0.44g, 5mol%/Penta) dosed in eight 0. 055g shots at 2h intervals. The time taken to reach a level of 5% Tris (the point at which the reaction is regarded as complete, and ready to go into the purification stage) was found to be 21h. After purification, the colour of the Anox 20 final product was found to be APHA 14 Comparative Example la Comparative Example 1 was repeated but with lithium hydroxide monohydrate (0.44g, 5mol%/Penta) added all at the beginning of the reaction. The time taken to reach a level of 5% Tris was found to be 28h. After purification, the colour of the Anox 20 final product was found to be APHA 20 Comparative Example lb Comparative example lwas repeated but with lithium hydroxide monohydrate (0. 15g, 1.7 mol%/Penta) and zinc octanoate (0.9g, 1. 2mol%/Penta) added together at the start. The time taken to reach a level of 5% Tris was found to be 27h. After purification, the colour of the Anox 20 final product was found to be APHA 16 These results are summarised in the following Table to illustrate the benefits of the inventive catalyst system
zinc diacetate; lithium acetate; at 180℃; for 1 - 23.5h;Product distribution / selectivity;
PP Base (247g, 15% excess), pentaerythritol (25g) and lithium acetate (0.75g, 3mol%/PE) were charged to 500ml litre 4-necked flask equipped with a stirrer, thermometer, pump inlet and distillation head fitted to a condenser, which in turn goes to a liquid-liquid exchanger containing water and cyclohexane. A pump is used to circulate the cyclohexane from the exchanger back into the reactor at a rate of about 1.6g/min, thus allowing continual distillation of cyclohexane + by-product methanol (the latter being extracted into water by the exchanger). The reaction mass was heated to 180C with distillation of cyclohexane and methanol. Samples were taken at regular intervals and analysed by HPLC, with results given in area % in the Table below. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 2 0. 37 10. 29 29. 95 0. 09 16. 36 40.86 4 0.39 5. 2 28. 38 0. 2 32. 67 31.54 6 0. 41 2. 83 23. 81 0. 41 44. 49 26.43 23 0. 44 0. 33 9. 54 0. 66 68. 83 18.34 47 0. 47 0. 08 4. 98 0. 92 75. 39 16.02 Comparative Example 3 As Comparative Example 2, but instead zinc octanoate (2.9g, 3mol%/PE) was used as catalyst with the following results. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 02 4. 10 0. 62 0. 00 0. 17 89.61 2 0. 00 10. 77 3. 36 0. 01 0. 15 77.15 3 0. 00 15. 63 7. 05 0. 02 0. 40 68. 47 4 0. 00 18. 25 11. 95 0. 01 0. 88 62.05 5 0. 00 18. 28 16. 29 0. 02 1. 52 58. 33 22. 8 0. 00 3. 90 30. 64 0. 71 28. 69 33.22 Example 2 As Comparative Example 2, but with lithium acetate (0.75g, 3mol%/PE) added at the beginning, and zinc acetate (1.43g, 3mol%/PE) added after 4h at 180C, with the following results. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 28 16. 88 18. 49 0. 04 3. 39 55.53 2 0. 40 10. 44 30. 22 0. 40 15. 32 40.53 3 0. 47 6. 96 30.02 0. 55 24. 96 34.75 4 0. 47 5. 34 28.65 0. 63 30. 51 32.08 5 0. 55 2. 92 24. 74 0. 77 40. 26 28.03 6 0. 66 1. 83 20. 54 0.87 47. 36 25.65 22. 3 02. 21 0.02 2. 07 1. 29 74. 53 15.27 Example 3 As Example 2, but with a reduced amount of PP Base (227.4g, 8% excess) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 30 17. 88 21. 13 0. 05 4. 42 50. 82 2 0.41 12. 02 31. 63 0. 41 15. 92 36.66 3 0.60 6. 72 29. 12 0. 75 33. 28 27.04 4 0. 67 6. 44 29. 06 0. 84 36. 25 26.24 5 0.81 3. 48 26. 25 0. 94 43. 25 22.47 6 0. 89 2. 36 22. 82 1. 09 49. 23 20. 30 7 1. 06 1. 61 19. 69 1. 22 55. 20 17.47 23. 3 2. 78 0. 08 4. 58 1. 67 76. 42 8. 86 Example 4 As Example 2, but with a lower amount of zinc acetate (0.72g, 1. 5mol%/PE) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 24 15. 87 22. 86 0. 07 5. 41 51.39 2 0.37 9. 59 30. 26 0. 41 17. 29 39.67 3 0.40 6.75 29.66 0.51 25. 16 35. 31 4 0.38 5. 15 28. 12 0.58 30. 92 32.63 5 0.52 3.18 24.96 0.69 39.20 28.99 6 0.61 1.90 20.72 0.80 46. 75 26.54 23.3 1.64 0.02 2.47 1.23 74. 42 15.68 Example 5 As Example 4, but with a lower amount of lithium acetate (0.38g, 1. 5mol%/PE) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1OH16. 39 14. 710032. 32 60.52 2 0. 14 12. 51 28. 61 0. 13 11. 81 43.90 3 0. 21 9. 02 30. 41 0. 24 19. 56 38.24 4 0. 23 6. 94 29. 83 0. 47 25. 34 35.01 50294. 48 28. 2105632. 66 31.46 6 0.30 2.97 25.29 0.66 40.88 27.33 22.5 1.03 0.01 1.84 1.16 75. 42 16.66
zinc(II) acetylacetonate; lithium acetate; for 4 - 10h;Product distribution / selectivity;
As Example 2, but with lithium acetate (0.2g, 1. 5mol%/l ? P base) added at the beginning and zinc acetylacetonate (0.73g, 1. 5mol%/PP base) added after 4h, with the following results obtained. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 3 0. 3 5. 0 27. 0 0. 6 28. 7 35. 8 4 0. 3 2. 9 23. 4 0. 7 39. 3 31. 0 6 0. 4 0. 5 10. 9 1. 0 61. 7 20. 9 10 0. 4 0 1. 4 1. 1 75. 1 18.
lithium hydroxide; zinc(II) octanoate; at 175℃; for 3 - 27h;Product distribution / selectivity;
PP Base (277g, 15% excess), pentaerythritol (28g) and lithium hydroxide monohydrate (0. 15g, 1. 7mol%/Penta) were charged to 500ml litre 4-necked flask equipped with a stirrer, thermometer, pump inlet and distillation head fitted to a condenser, which in turn goes to a liquid-liquid exchanger containing water and cyclohexane. A pump is used to circulate the cyclohexane from the exchanger back into the reactor at a rate of about 0.4g cyclohexane/PP Base g per hour, thus allowing continual distillation of cyclohexane + by-product methanol (the latter being extracted into water by the exchanger). The reaction mass was heated to 175C with distillation of cyclohexane and methanol. Two shots of zinc octanoate (0.448g, 0. 6mol%/Penta) were added after 5 and 12h. Samples were taken at regular intervals and analysed by HPLC, with results given in area% in the Table below. Time (hrs) PP Acid Disub Tris Anox 20 PP Base 3 0. 4 7. 9 31. 2 27. 3 32. 7 5 0. 4 5. 0 27. 5 38. 6 28. 0 7 0. 4 1. 9 19. 7 56. 2 21. 5 9 0. 4 0. 9 13. 1 66. 8 18. 4 12oui0. 6 7. 8 74. 2 16. 1 14 0_5 03 4. 9 78. 8 15. 0 16 0_5 0. 3 3. 7 80. 2 14. 7 After purification (dilution with cyclohexane, washing, separation of the aqueous layer, drying and crystallisation from cyclohexane), the colour of the Anox 20 final product was found to be APHA 6. Example la Example 1 was repeated but with a reduced excess of PP Base (260g, 8% excess), and with just one shot of zinc octanoate (0.9g, 1. 2mol%/Penta) after 5h. The results are provided in the Table below. Time (hrs) PP Acid Disub Tris Anox 20 PP Base 3 0.4 5.8 29.5 39.4 24.0 5 0. 4 4. 7 27. 2 45. 4 21. 5 7 0.4 2. 2 22. 0 56. 8 17. 6 9 0.4 1. 4 16. 9 65. 1 15. 5 12 0. 5 0. 8 11. 7 73. 5 12. 7 14 0. 6 0. 5 8. 5 77. 9 11. 6 19 0. 7 0. 3 5 80. 0 10. 9 After purification, the colour of the Anox 20 final product was found to be APHA 5 Comparative Example 1 Example 1 was repeated but with lithium hydroxide monohydrate (0.44g, 5mol%/Penta) dosed in eight 0. 055g shots at 2h intervals. The time taken to reach a level of 5% Tris (the point at which the reaction is regarded as complete, and ready to go into the purification stage) was found to be 21h. After purification, the colour of the Anox 20 final product was found to be APHA 14 Comparative Example la Comparative Example 1 was repeated but with lithium hydroxide monohydrate (0.44g, 5mol%/Penta) added all at the beginning of the reaction. The time taken to reach a level of 5% Tris was found to be 28h. After purification, the colour of the Anox 20 final product was found to be APHA 20 Comparative Example lb Comparative example lwas repeated but with lithium hydroxide monohydrate (0. 15g, 1.7 mol%/Penta) and zinc octanoate (0.9g, 1. 2mol%/Penta) added together at the start. The time taken to reach a level of 5% Tris was found to be 27h. After purification, the colour of the Anox 20 final product was found to be APHA 16 These results are summarised in the following Table to illustrate the benefits of the inventive catalyst system
zinc diacetate; lithium acetate; at 180℃; for 1 - 23.5h;Product distribution / selectivity;
PP Base (247g, 15% excess), pentaerythritol (25g) and lithium acetate (0.75g, 3mol%/PE) were charged to 500ml litre 4-necked flask equipped with a stirrer, thermometer, pump inlet and distillation head fitted to a condenser, which in turn goes to a liquid-liquid exchanger containing water and cyclohexane. A pump is used to circulate the cyclohexane from the exchanger back into the reactor at a rate of about 1.6g/min, thus allowing continual distillation of cyclohexane + by-product methanol (the latter being extracted into water by the exchanger). The reaction mass was heated to 180C with distillation of cyclohexane and methanol. Samples were taken at regular intervals and analysed by HPLC, with results given in area % in the Table below. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 2 0. 37 10. 29 29. 95 0. 09 16. 36 40.86 4 0.39 5. 2 28. 38 0. 2 32. 67 31.54 6 0. 41 2. 83 23. 81 0. 41 44. 49 26.43 23 0. 44 0. 33 9. 54 0. 66 68. 83 18.34 47 0. 47 0. 08 4. 98 0. 92 75. 39 16.02 Comparative Example 3 As Comparative Example 2, but instead zinc octanoate (2.9g, 3mol%/PE) was used as catalyst with the following results. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 02 4. 10 0. 62 0. 00 0. 17 89.61 2 0. 00 10. 77 3. 36 0. 01 0. 15 77.15 3 0. 00 15. 63 7. 05 0. 02 0. 40 68. 47 4 0. 00 18. 25 11. 95 0. 01 0. 88 62.05 5 0. 00 18. 28 16. 29 0. 02 1. 52 58. 33 22. 8 0. 00 3. 90 30. 64 0. 71 28. 69 33.22 Example 2 As Comparative Example 2, but with lithium acetate (0.75g, 3mol%/PE) added at the beginning, and zinc acetate (1.43g, 3mol%/PE) added after 4h at 180C, with the following results. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 28 16. 88 18. 49 0. 04 3. 39 55.53 2 0. 40 10. 44 30. 22 0. 40 15. 32 40.53 3 0. 47 6. 96 30.02 0. 55 24. 96 34.75 4 0. 47 5. 34 28.65 0. 63 30. 51 32.08 5 0. 55 2. 92 24. 74 0. 77 40. 26 28.03 6 0. 66 1. 83 20. 54 0.87 47. 36 25.65 22. 3 02. 21 0.02 2. 07 1. 29 74. 53 15.27 Example 3 As Example 2, but with a reduced amount of PP Base (227.4g, 8% excess) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 30 17. 88 21. 13 0. 05 4. 42 50. 82 2 0.41 12. 02 31. 63 0. 41 15. 92 36.66 3 0.60 6. 72 29. 12 0. 75 33. 28 27.04 4 0. 67 6. 44 29. 06 0. 84 36. 25 26.24 5 0.81 3. 48 26. 25 0. 94 43. 25 22.47 6 0. 89 2. 36 22. 82 1. 09 49. 23 20. 30 7 1. 06 1. 61 19. 69 1. 22 55. 20 17.47 23. 3 2. 78 0. 08 4. 58 1. 67 76. 42 8. 86 Example 4 As Example 2, but with a lower amount of zinc acetate (0.72g, 1. 5mol%/PE) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1 0. 24 15. 87 22. 86 0. 07 5. 41 51.39 2 0.37 9. 59 30. 26 0. 41 17. 29 39.67 3 0.40 6.75 29.66 0.51 25. 16 35. 31 4 0.38 5. 15 28. 12 0.58 30. 92 32.63 5 0.52 3.18 24.96 0.69 39.20 28.99 6 0.61 1.90 20.72 0.80 46. 75 26.54 23.3 1.64 0.02 2.47 1.23 74. 42 15.68 Example 5 As Example 4, but with a lower amount of lithium acetate (0.38g, 1. 5mol%/PE) used. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 1OH16. 39 14. 710032. 32 60.52 2 0. 14 12. 51 28. 61 0. 13 11. 81 43.90 3 0. 21 9. 02 30. 41 0. 24 19. 56 38.24 4 0. 23 6. 94 29. 83 0. 47 25. 34 35.01 50294. 48 28. 2105632. 66 31.46 6 0.30 2.97 25.29 0.66 40.88 27.33 22.5 1.03 0.01 1.84 1.16 75. 42 16.66
zinc(II) acetylacetonate; lithium acetate; for 4 - 10h;Product distribution / selectivity;
As Example 2, but with lithium acetate (0.2g, 1. 5mol%/l ? P base) added at the beginning and zinc acetylacetonate (0.73g, 1. 5mol%/PP base) added after 4h, with the following results obtained. Time (hrs) PP Acid Disub Tris De-butyl A20 PP Base 3 0. 3 5. 0 27. 0 0. 6 28. 7 35. 8 4 0. 3 2. 9 23. 4 0. 7 39. 3 31. 0 6 0. 4 0. 5 10. 9 1. 0 61. 7 20. 9 10 0. 4 0 1. 4 1. 1 75. 1 18.
Example 3; Continuous Processing of Hindered Phenolic Esters (Mixture of n-butyl and Methyl Acrylate) with a Continuous Phenoxide Formation; The same procedure of Example 1 is used except that in the four-reactor system of part two, n-butyl acrylate is fed into the first reactor at a rate of 1.52 kg/hr and at simultaneously, methyl acrylate is fed into the same reactor at a rate of 0.08 kg/hr. The use of a mixture of n-butyl and methyl acrylate in the process can preclude crystallation of the hindered ester-substituted phenol.
(A) Preparation of 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionylhydrazine 160 g of methanol and 117 g (0.4 moles) of methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate are charged into a 500 ml four-necked flask equipped with a mechanical stirrer, thermometer and reflux condenser connected to a phase separator, and maintained under stirring: the mixture is heated to 45 C.-50 C. and 80.1 g (1.6 moles) of hydrated hydrazine at 64% are gradually added. The resulting mixture is maintained under stirring and reflux heated to 72 C. for 6.5 hours and the conversion of the ester to monoacylhydrazine proves to be over 98%. After 6.5 hours there is the formation of a little precipitate consisting of monoacylhydrazine. The mixture is slowly cooled to 50 C., 10 g of water are added and it is finally cooled to 20 C. in 8 hours and filtered obtaining a cake which is washed with 150 g of water to remove the excess hydrazine. This humid cake is equal to 167.1 g with a dry residue of 68.7% corresponding to 114.8 g at 100%. The gas-chromatographic purity of a small portion dried aside at 90 C. gave a value equal to 99.4%. The reaction yield, referring to the quantity of methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate charged, is equal to 98.1%.
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid isooctyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
99% by weight
With tin;
EXAMPLE 1 Isooctyl 3,5-Di-tert-butyl-4-hydroxyhydrocinnamate In a three-necked, round-bottomed flask fitted with a stirrer, thermometer, reflux condenser with a trap to collect distilled off methanol and later isooctanol and a vacuum connection are added 200 g (0.684 mole) of methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 178 g (1.37 moles, 100% excess) of isooctanol (Exxal-8, Exxon) and 0.05 g (0.0000826 mole; 50 ppm of tin in final product) of butyltin tris-(2-ethylhexanoate) (Fascat 9102, Elf-Atochem). The reaction mixture is subjected to a reduced pressure of 400 mm Hg and the flask is heated to 140-150 C. Methanol begins to be evolved and is collected in the trap receiver. When the reaction mixture reaches 160 C., reflux of isooctanol is observed and becomes vigorous at 170-180 C. while the evolution of methanol subsides. At this point, the excess isooctanol is then stripped into the trap receiver and the pressure in the system is ultimately reduced to 5 mm Hg. When all the excess isooctanol is removed, the residue in the flask is cooled under nitrogen and is the desired title compound in essentially quantitative yield (over 99% by weight). The product is "water-white" and contains less than 1% by weight of starting methyl ester and less than 0.1% by weight of isooctanol.
99% by weight
With tin;
Example 1 Isooctyl 3,5-Di-tert-butyl-4-hydroxyhydrocinnamate In a three-necked, round-bottomed flask fitted with a stirrer, thermometer, reflux condenser with a trap to collect distilled off methanol and later isooctanol and a vacuum connection are added 200 g (0.684 mole) of methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 178 g (1.37 moles, 100% excess) of isooctanol (Exxal-8, Exxon) and 0.05 g (0.0000826 mole; 50 ppm of tin in final product) of butyltin tris-(2-ethylhexanoate) (Fascat 9201, Elf-Atochem). The reaction mixture is subjected to a reduced pressure of 400 mm Hg and the flask is heated to 140-150C. Methanol begins to be evolved and is collected in the trap receiver. When the reaction mixture reaches 160C, reflux of isooctanol is observed and becomes vigorous at 170-180C while the evolution of methanol subsides. At this point, the excess isooctanol is then stripped into the trap receiver and the pressure in the system is ultimately reduced to 5 mm Hg. When all the excess isooctanol is removed, the residue in the flask is cooled under nitrogen and is the desired title compound in essentially quantitative yield (over 99% by weight). The product is 'water-white' and contains less than 1% by weight of starting methyl ester and less than 0.1% by weight of isooctanol.
2-Methoxypropyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Reference Example 2 2-Methoxypropyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate The title compound was prepared from methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and propylene glycol monomethyl ether, by a procedure analogous to that of Reference Example 10. White powder with mellting point 73-74 C.
Comparative Example 1 2-Methoxyethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate The title compound was prepared from 90 g of toluene, 102.4 g of methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 18.2 g of ethylene glycol monomethyl ether and 0.35 g of sodium methoxide, by a procedure analogous to that of Example 10. Yield 42.2 g. Melting point 62-64 C.
EXAMPLE 1 2,2-Bis[4-(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy))ethoxyphenyl]propane Methyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (6.42 g) was added to a flask equipped with a reflux condenser heated to 65 C. with hot water. The material was heated to 140 C. under N2 with magnetic stirring. Sodium methoxide (0.054 g) was added and a vacuum (10 mm) was applied. After 15 min., the vacuum was broken with N2 and 2,2-bis[4-(2-hydroxy)ethoxyphenyl]propane (3.16 g) was added. Vacuum was reapplied and temperature was slowly increaded to 160 C. After 4 hrs., the reaction was quenched with acetic acid and crystallized from isopropanol to give 7.5 g (89%) of the desired product, mp 104-106 C. Calculated for C53 H72 O8: C, 76.07; H, 8.61. Found: C, 75.94; H, 8.66.
EXAMPLE 1 Preparation of Intermediate 3-(3',5'-Di-tert-butyl-4'-hydroxyphenyl)-1-propanol A solution of methyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate (117 g, 0.4 mol) in 200 ml of anhydrous ether was added dropwise to a mixture of lithium aluminum hydride (17 g, 0.45 mol) and anhydrous ether (800 ml) under an inert atmosphere with ice-water cooling. After the addition was completed, the reaction mixture was heated at reflux temperature for one hour, then cooled to room temperature. To the cooled mixture was added dropwise 80 ml of 3% sodium hydroxide aqueous solution with vigorous stirring and with ice-water cooling. After the addition was completed, the mixture was stirred at room temperature for 30 minutes. A white precipitate was separated by filtration and washed with ether. The filtrate and washings were combined and evaporated. The residue was vacuum distilled to give 101 g (95%) of the product.
(4) Octadecyl 3-(3,5-di-tertbutyl-4-hydroxyphenyl)-propionate was prepared from 124.8 g (0.427 mole) of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 88.8 g (0.328 mole) of octadecyl alcohol and 0.13 g (0.0007 mole) of monobutyltin oxide. To the solution (214 g) of it was added 35 g of synthetic magnesium silicate (manufactured by Mizusawa Chemical Co.), and the solution was stirred at 60 C. for 0.5 hour. The organic layer wa separated by filtration. The residual tin content was 3 ppm (removal rate: 99.2%).
N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With 1-methyl-pyrrolidin-2-one;
EXAMPLE 5 To a reaction vessel equipped with a condenser, a thermometer, a trap, a nitrogen sparge tube and a mechanical stirrer are added 43 g (10 mole % excess) methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 5 g 1,3-diaminopropane and 5 ml of N-methylpyrrolidone (NMP). Then 0.1 g of lithium amide is added with agitation and the reaction mixture is heated to 100 C. at atmospheric pressure while continuously sparging with nitrogen gas at a rate of 0.3 L/min. for 2.5 hours. Analysis by high pressure liquid chromatography indicated that 90% of 1,3-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamido] propane is obtained.
(a) Preparation of oleyl beta-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate 292.4 g (1 mole) of methyl beta-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate and 383.6 g (1 mole) of oleyl alcohol are initially taken in 50 ml of toluene and are heated at 120 C., so that the toluene has distilled off in the course of one hour. 2.5 g of lithium amide are then added and the methanol which is formed is distilled off at 80 C. The mixture is then heated to 120 C. and is kept at this temperature for 4 hours. The reaction is monitored by thin layer chromatography. When the reaction is complete, the reaction mixture is dissolved in 200 ml of toluene, neutralised with 12 ml of concentrated HCl and then washed with twice 200 ml of water. The organic phase is separated off, dried over Na2 SO4 and concentrated on a rotary evaporator. The residue is dried at 80 C. in a high vacuum. This gives a slightly yellowish oil (yield: 95% of theory)
1-[2-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionyloxy]-ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxy]-2,2,6,6-tetramethyl-piperidine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In toluene;
EXAMPLE 1 1-[2-{3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-4-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}-2,2,6,6-tetramethylpiperidine (Compound No. 1) A mixture of 2.0 g of 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 6.4 g of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 0.4 g of lithium amide was refluxed in 300 ml of toluene for 8 hours, while removing continuously an azeotropic mixture consisting of toluene and methanol formed in situ. During the reaction, the volume of the reaction mixture was maintained at about 300 ml by adding continuously toluene in an amount corresponding to the azeotropic mixture removed. After completion of the reaction, the reaction mixture was poured into ice-water and the toluene layer was separated and dried over anhydrous magnesium sulfate. After the toluene was evaporated under reduced pressure, the resulting residue was purified by column chromatography through silica gel eluted with benzene, then by recrystallization from n-hexane, giving the desired compound in the form of white crystals melting at 137-138.5 C.
3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid allyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In toluene;
EXAMPLE 5 3-(3,5-Di-t-butyl-4-hydroxyphenyl)-propionic acid allyl ester 0.2 g of lithium amide and in the course of 5 hours 38 g of allyl alcohol are added at 150 C. under nitrogen to 146 g of 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic acid methyl ester. After completion of the addition, stirring is maintained at 150 C. for a further 10 hours. The brownish reaction mixture is cooled to about 100 C., and 150 ml of toluene, 0.5 g of concentrated acetic acid and 10 g of "Celite Hyflow Supercel" (product of Johns Manville Corp., USA) are added. There is thus obtained, after filtration and then removal of the solvent in vacuo, the title compound in crystalline form, m.p. about 40 C.
3,5-Di-tert-butyl-4-hydroxy-dihydrocinnamic acid(2,2,6,6-tetramethylphosphorinan-4-yl)ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
3.9 g (33%)
EXAMPLE 4 3,5-Di-tert-butyl-4-hydroxy-dihydrocinnamic acid(2,2,6,6-tetramethylphosphorinan-4-yl)ester A flask equipped with a Dean-Stark trap and a dry ice condenser was charged with 4.7 grams (0.027 mol) of 4-hydroxy-2,2,6,6-tetramethyl-1H-phosphorinane, 7.9 grams (0.27 mol) of methyl-3,5-di-tert-butyl-4-hydroxy-dihydrocinnamate and 20 mg (2.5 mol) of lithium hydride. The mixture was stirred under nitrogen and heated at 120-135 C. and 50 mm Hg until 1.2 mls (100% of theory) of distillate were collected. The reaction mixture was chromatographically purified to give 3.9 g (33%) of white solid, mp 81-84 C. Calcd. for C26 H42 O3 P: C, 72.0; H, 9.8; P, 7.1. Found: C, 72.1; H, 9.6; P, 6.9.
EXAMPLE 3 Tetraethylene glycol bis{3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate} 4.1 grams of sodium methylate is added to 48.5 grams of tetraethylene glycol at 60C in a dry nitrogen atmosphere and stirred until dissolved. 100 grams of methyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate is added and the reaction mixture heated at 150-154C. 10.2 ml of methanol is collected in a Dean Stark trap over a period of 2 hours. The reaction mixture is then heated at 20 mm Hg. pressure for an additional 25 hours during which an additional 9.5 ml of methanol is collected. The reaction mixture is dissolved in a solvent mixture of about 700 ml of benzene and ether, and neutralized with glacial acetic acid. The solution is then washed with water, sodium carbonate solution, water, and finally dried over sodium sulfate. The crude product is recovered by removing the benzene and ether solvent under reduced pressure. Unreacted methyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl) propionate and other volatile impurities are removed by distillation with a wiped film evaporator, the wall temperature being first 180 to 200C, then 255C, the pressure being in the range of 1 to 5 microns. The product thus isolated is a syrupy liquid.
EXAMPLE 1 methoxytriethylene glycol 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate The aparatus was flushed with nitrogen and charged with 29.2 g of methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 41.1 g of methoxytriethyleneglycol and 10.2 ml of 40% methanol solution of benzyltrimethylammonium methoxide. The reaction was heated for 21/2 hours between 92 and 105 C. at atmospheric pressure and for an additional 1/2 hour at 100 C. at 1 mm pressure. After cooling, the reaction mixture was neutralized with 2.4 ml of glacial acetic acid. The reaction mixture was distilled and the fraction boiling at 200-210 C. at a pressure of 1 to 3 mu was collected as the product. The refractive index of the product at 25 C. was 1.5034. Analysis for C24 H40 O6: % Calculated: C, 67.89; H, 9.50; % Found: C, 68.23; H, 9.36.
methoxytriethyleneglycol 3-(3'-methyl-5'-t-butyl-4'-hydroxyphenyl)propionate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid methyl ester;
In a similar fashion utilizing an equivalent amount of methyl 3-(3'-methyl-5'-t-butyl-4'-hydroxyphenyl)propionate in the above procedure in place of the designated quantity of methyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, there is obtained methoxytriethyleneglycol 3-(3'-methyl-5'-t-butyl-4'-hydroxyphenyl)propionate.
β-methoxyethyl 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In methyl 3-(4-hydroxy-3,5-dimethylphenyl)propanoate;
In a similar fashion utilizing an equivalent amount of methyl-3(3',5'-dimethyl-4'-hydroxyphenyl)propionate in the above procedure in place of the designated quantity of methyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, there is obtained beta-methoxyethyl 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionate.
EXAMPLE 2 beta-methoxyethyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate The reaction flask was flushed with nitrogen and charged with 29.2 g of methyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, 22.8 g of beta-methoxyethanol and 10.2 ml of 40% methanol solution of benzyltrimethylammonium methoxide. The reaction mixture was heated under nitrogen at atmospheric pressure for approximately 1 hour at a temperature of 80-100 C. After cooling, the reaction mixture was neutralized with 2.4 ml of glacial acetic acid. The excess of beta-methoxyethanol was distilled under vacuum of 55 mm pressure at 55 C. The product was vacuum distilled and had a boiling point of 160-165 C. at 0.3 mm pressure. Analysis for C20 H32 O4: % Calculated: C, 71.39; H, 9.59; % Found: C, 71.12; H, 9.24.
EXAMPLE 16 3-[3-Di{2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl}amino-2-hydroxypropyl]-7,7,8,9,9-pentamethyl-2,4-dioxo-1,3,8-triazaspiro[4.5]decane (Compound No. c-17) Using 2.0 g of 3-[3-di(2-hydroxyethyl)amino-2-hydroxypropyl]-7,7,8,9,9-pentamethyl-2,4-dioxo-1,3,8-triazaspiro-[4.5]decane prepared in Example 4 and 3.0 g of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, the reaction and the post-treatment were carried out according to the same procedures as in Example 15 to give a viscous oily substance, which was purified through a silica gel column chromatography using ethyl acetate as the eluent to afford the desired compound as a pale yellow viscous oily substance. The compound exhibited the Rf value of 0.55 in the silica gel thin layer chromatography using ethyl acetate as the developing solvent.
EXAMPLE 2 2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]-8-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro[4.5]decane (Compound No. 16) A mixture of 5.5 g of 2-hydroxymethyl-8-(2-hydroxyethyl)-7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro[4.5]decane, 14 g of methyl 3-(3,5-di-tert-butyl-4-hydroxylphenyl)propionate and 0.25 g of lithium amide was heated for 2 hours in 200 ml of toluene, under argon stream. During the reaction, 120 ml of toluene was removed together with methanol formed in situ. After completion of the reaction, the reaction mixture was poured into water and extracted with benzene. The extract was dried over anhydrous potassium carbonate and the solvent was distilled out from the extract. The residue was purified by column chromatography through silica gel eluted first with benzene, then with a 10:5:4 by volume mixture of n-hexane, benzene and ethyl acetate, giving the desired compound in the form of a vitreous substance softening at 49-53 C. The compound had an Rf value of 0.37 on thin-layer chromatography on silica gel using a 7:2:1 by volume mixture of n-hexane, benzene and ethyl acetate as developing solvent.
3-hydroxymethyl-3-ethyl-9-(2-hydroxyethyl)-8,8,10,10-tetramethyl-1,5-dioxa-9-azaspiro[5.5]undecane[ No CAS ]
[ 6386-38-5 ]
3-[3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]-3-ethyl-9-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxy}ethyl]-8,8,10,10-tetramethyl-1,5-dioxa-9-azaspiro[5.5]undecane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In toluene;
EXAMPLE 3 3-[3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]-3-ethyl-9-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxy}ethyl]-8,8,10,10-tetramethyl-1,5-dioxa-9-azaspiro[5.5]undecane (Compound No. 12) A mixture of 6.3 g of 3-hydroxymethyl-3-ethyl-9-(2-hydroxyethyl)-8,8,10,10-tetramethyl-1,5-dioxa-9-azaspiro[5.5]undecane, 14 g of methyl 3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate and 0.25 g of lithium amide was refluxed for 2 hours in 150 ml of toluene under argon stream. During the reaction, 120 ml of toluene was removed together with methanol formed in situ. After completion of the reaction, the reaction mixture was treated in the similar manner as in Example 3, giving the desired compound in the form of a white powder softening at 51-56 C. The compound had Rf value of 0.41 on thin-layer chromatography on silica gel using a 7:2:1 by volume mixture of n-hexane, benzene and ethyl acetate as developing solvent.
2,2,4,4,14,14,16,16-Octamethyl-3,15-bis[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-7,11,18,21-tetraoxa-3,15-diazatrispiro[5.2.2.5.2.2]heneicosane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In hexane; ethyl acetate; toluene; benzene;
EXAMPLE 4 2,2,4,4,14,14,16,16-Octamethyl-3,15-bis[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-7,11,18,21-tetraoxa-3,15-diazatrispiro[5.2.2.5.2.2]heneicosane (Compound No. 6) A mixture of 20 g of 2,2,4,4,14,14,16,16-octamethyl-3,15-bis(2-hydroxyethyl)-7,11,18,21-tetraoxa-3,15-diazatrispiro[5.2.2.5.2.2]heneicosane, 26 g of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 2 g of lithium amide was refluxed for 8 hours in 400 ml of toluene under argon stream. Following the procedures in Example 1, the residue was purified first by column chromatography through silica gel with a 9:1 by volume mixture of benzene and ethyl acetate, then by recrystallization from a 4:1 by volume mixture of n-hexane and benzene, giving the desired compound in the form of pale yellow crystals melting at 176-178 C.
3,8-Bis[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-7,7,9,9-tetramethyl-2,4-dioxo-1,3,8-triazaspiro[4.5]decane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium methylate; In 5,5-dimethyl-1,3-cyclohexadiene;
EXAMPLE 1 3,8-Bis[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-7,7,9,9-tetramethyl-2,4-dioxo-1,3,8-triazaspiro[4.5]decane (Compound No. 1) A mixture of 2.9 g of 3,8-bis(2-hydroxyethyl)-7,7,9,9-tetramethyl-2,4-dioxo-1,3,8-triazaspiro [4.5]decane, 6.4 g of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 0.3 g of sodium methoxide was refluxed for 8 hours in 300 ml of xylene, while removing 250 ml of xylene together with methanol formed in situ. After completion of the reaction, xylene was evaporated from the reaction under reduced pressure and the resulting residue was recrystallized from ligroin, giving the desired compound in the form of white crystals melting at 178-179 C.
EXAMPLE 2 292 g (1.0 mol) of methyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate and 275.4 g (1.02 mols) of stearyl alcohol are introduced into a 1.5 liter flask, under nitrogen. The flask is evacuated, for dehydration, and the reaction mixture is stirred at 90 C. for 30 minutes. The flask is then let down with nitrogen and 1.0 g (0.004 mol) of di-butyl-tin oxide is added. The flask is evacuated and the melt is heated to 155 C. Most of the methanol formed in the reaction thereby distils off. A higher vacuum is now applied and stirring is continued at 155 C. for 5 hours. The mixture is cooled to 110 C., 10 g of Tonsil AC are added and the mixture is kept at 107 to 110 C. for 30 minutes. The suspension is clarified over a prewarmed Hyflo suction filter. The clarified melt is left to solidify and then comminuted. 525 g (99% of theory) of octadecyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate are obtained.
EXAMPLE 1 292.0 g (1.0 mol) of methyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate, 275.4 g (1.02 mol) of stearyl alcohol and 130 g of toluene are introduced into a 1.5 liter flask, under nitrogen. The mixture is heated, and dehydrated azeotropically. It is cooled to 75 C. and 2.6 g of hydroquinone and 1.0 g (0.004 mol) of dibutyl-tin oxide are added. The mixture is now heated to 170 C., and methanol is thereby distilled off over a dephlegmator charged with warm water at 75 C. As soon as the internal temperature has reached 170 C., the dephlegmator is emptied, and distillation is continued at a constant internal temperature of 170 C. for a further 3 hours. The toluene thereby distilled off is replaced by a total of about 550 g of new toluene. The solution is cooled to 110 C. 10 g of Montmorillonit-Erde K-10 are added, the mixture is stirred at 107 to 110 C. for 30 minutes, the suspension is clarified over a Hyflo and the filtrate is evaporated in a rotary evaporator. The melt which remains is poured into a dish and seeded at about 50 C., and the crystal mass obtained after cooling is comminuted. 530 g (99.9% of theory) of octadecyl 3-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate are obtained.
Example 3: Continuous Processing of Hindered Phenolic Esters (mixture of n-butyl and methyl acrylate) with a Continuous Phenoxide FormationThe same procedure of Example 1 is used except that in the four-reactor sys- tern of part two, n-butyl acrylate is fed into the first reactor at a rate of 1.52 kg/hr and at simultaneously, methyl acrylate is fed into the same reactor at a rate of 0.08 kg/hr.The use of a mixture of n-butyl and methyl acrylate in the process can preclude crystallation of the hindered ester-substituted phenol
With oxygen; 5,15,10,20-tetraphenylporphyrin; In chloroform; at 20℃; for 16h;Irradiation;
General procedure: Para-substituted phenol (0.1g) was dissolved in chloroform (5 ml) and tetraphenyl porphin (5mg, 0.01 mmol) was added. Oxygen was bubbled through the resulting solution for 1 min andit was then kept under an oxygen atmosphere by connection to an oxygen-filled balloon. Thesolution was irradiated using six LED lights for the required reaction time (between 16-48 h).The resulting solution was reduced to dryness and purified directly by columnchromatography to give the desired peroxy quinol.
3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)propionamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With boric acid; In toluene; for 15h;Dean-Stark; Inert atmosphere; Reflux; Molecular sieve;
Example 12: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(4- phenylamino-phenyl)-propionamide using 3-(3, 5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester In a set-up of Dean-Stark apparatus, 1.0 g of N-Phenyl -benzene- 1 ,4-diamine is dissolved in 40 ml of anhydrous toluene. 1.3 g of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)- propionic acid methyl ester and a catalytic amount of boric acid (0.024g) are added to the flask. 10 g of 4 A0 molecular sieves are added in the dean stark to absorb the eliminated methanol during the course of reaction. The reaction mixture is refluxed under argon atmosphere for 15 hours. The crude product thus obtained is purified to get 3-(3,5-Di-tert- butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)-propionamide.
3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)propionamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With boric acid; In toluene; for 15h;Dean-Stark; Inert atmosphere; Reflux; Molecular sieve;
Example 15: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l -methyl- heptyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3, 5-Di-tert-butyl-4-hydroxy- pheny I) -propionic acid methyl ester In a set-up of Dean-Stark apparatus, 1.0 g of N-(l -Methyl -heptyl)-N'-phenyl- benzene- 1 ,4-diamine is dissolved in 40 ml of anhydrous toluene. 1.3 g of 3-(3,5-Di-tert-butyl- 4-hydroxy-phenyl)-propionic acid methyl ester and a catalytic amount of boric acid (0.024g) are added to the flask. 10 g of 4 A0 molecular sieves are added in the dean stark to absorb the eliminated methanol during the course of reaction. The reaction mixture is refluxed under argon atmosphere for 15 hours. The crude product thus obtained is purified to get 3-(3,5-Di- tert-butyl-4-hydroxy-phenyl)-N-(l -methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamide.
N-(1,4-dimethylpentyl)-N'-phenyl-p-phenylenediamine[ No CAS ]
[ 6386-38-5 ]
3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-N-(1,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)propionamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With boric acid; In toluene; for 15h;Dean-Stark; Inert atmosphere; Reflux; Molecular sieve;
Example 9: Synthesis of 3 -(3, 5-Di-tert-butyl-4-hydroxy-phenyl)-N- ( 1, 4-dimethyl- pentyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- pheny I) -propionic acid methyl ester In a set-up of Dean-Stark apparatus, 1.0 g of N-(l ,4-Dimethyl-pentyl)-N'-phenyl- benzene- 1 ,4-diamine is dissolved in 40 ml of anhydrous toluene. 1.4 g of 3-(3,5-Di-tert-butyl- 4-hydroxy-phenyl)-propionic acid methyl ester and a catalytic amount of boric acid (0.024g) are added to the flask. 10 g of 4 A0 molecular sieves are added in the dean stark to absorb the eliminated methanol during the course of reaction. The reaction mixture is refluxed under argon atmosphere for 15 hours. The crude product thus obtained is purified to get 3-(3,5-Di- tert-butyl-4-hydroxy-phenyl)-N-(l ,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)- propionamide.
3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)propionamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With boric acid; In toluene; for 15h;Dean-Stark; Inert atmosphere; Reflux; Molecular sieve;
Example 10: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l ,3-dimethyl- butyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- pheny I) -propionic acid methyl ester In a set-up of Dean-Stark apparatus, 1.0 g of N-(l ,3-Dimethyl-butyl)-N'-phenyl- benzene- 1 ,4-diamine is dissolved in 40 ml of anhydrous toluene. 1.3 g of 3-(3,5-Di-tert-butyl- 4-hydroxy-phenyl)-propionic acid methyl ester and a catalytic amount of boric acid (0.024g) are added to the flask. 10 g of 4 A0 molecular sieves are added in the dean stark to absorb the eliminated methanol during the course of reaction. The reaction mixture is refluxed under argon atmosphere for 15 hours. The crude product thus obtained is purified to get 3-(3,5-Di- tert-butyl-4-hydroxy-phenyl)-N-( 1 ,3 -dimethyl-butyl)-N-(4-phenylamino-phenyl)- propionamide.
3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)propionamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With boric acid; In toluene; for 15h;Dean-Stark; Inert atmosphere; Reflux; Molecular sieve;
Example 11 : Synthesis of 3- (3, 5-Di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N- (4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)- propionic acid methyl ester In a set-up of Dean-Stark apparatus, 1.0 g of N-Isopropyl-N'-phenyl-benzene- 1 ,4- diamine is dissolved in 40 ml of anhydrous toluene. 1.3 g of 3-(3,5-Di-tert-butyl-4-hydroxy- phenyl)-propionic acid methyl ester and a catalytic amount of boric acid (0.024g) are added to the flask. 10 g of 4 A0 molecular sieves are added in the dean stark to absorb the eliminated methanol during the course of reaction. The reaction mixture is refluxed under argon atmosphere for 15 hours. The crude product thus obtained is purified to get 3-(3,5-Di-tert- butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)-propionamide.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
