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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
Ascorbyl Palmitate is an ester formed from ascorbic acid and palmitic acid creating a fat-soluble form of vitamin C, it is also used as an antioxidant food additive.
Synonyms: L-Ascorbic acid 6-hexadecanoate; 6-O-Palmitoyl-L-ascorbic acid; HSDB 418
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CAS No. : | 137-66-6 |
Formula : | C22H38O7 |
M.W : | 414.53 |
SMILES Code : | OC([C@H](O1)[C@H](COC(CCCCCCCCCCCCCCC)=O)O)=C(O)C1=O |
Synonyms : |
L-Ascorbic acid 6-hexadecanoate; 6-O-Palmitoyl-L-ascorbic acid; HSDB 418
|
MDL No. : | MFCD00005377 |
InChI Key : | QAQJMLQRFWZOBN-LAUBAEHRSA-N |
Pubchem ID : | 54680660 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H332-H335 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; at 18 - 35℃;Inert atmosphere; | (1) 100 ml (about 184 g) 99-99.5% sulfuric acid was added to 250 ml four-neck flask with stirring, 35 g of palmitic acid was added at 30-35C dissolved with stirring for 0.5-1 hour. The temperature was dropped to 20-25C under protection of nitrogen, 17.6 grams of vitamin C was added with stirring, and stirring was stopped until completely dissolved, and insulated at 18-20C for 48 hours to obtain reaction liquid vitamin C palmitate. (2) The temperature was controlled to below 40C , the reaction solution was slowly poured into 200 ml 4-neck flask placed in ice-bath containing 200 ml cooling water. 700 ml of toluene was added and then subjected to extraction, heated to 60C and cooled naturally with stirring, when the temperature of the system was reduced to about 40C, stratified, and lower waste acid was separated leaving the toluene layer. (3) To the toluene layer 30-35 200 ml of water was added, stirred at 30-35C for 3 hours, crystallized at 30-35C for three hours, cooled in ice-water at 10-15C, stirred for one hour and filtered. The filter cake was washed with 50 ml of toluene, and then washed with 500 ml of water at 30-35C. (4) The filter cake was added to 500 ml water at 30-35C for 1 hour, filtered, and then washed with 200 ml water at 30-35C and the effluent water PH =7 was drained, discharged, and air-dried at room temperature for one day to constant weight. The crude product of vitamin C palmitate 33-34 g was obtained. Yield of 79.7-82.1%. (5) Take the above crude vitamin C palmitate, dissolved in 7.5 times the volume of 95% ethanol at 35-40 deg. C, filtered, washed with 0.5 volume of 95% ethanol and filtrate had crystallized, heated at 35-40C until fully dissolved and transferred to 500 ml 4-neck flask, rapidly cooled to -25--20C, crystallized by stirring for 3 hours, filtered, the filter cake was washed with 95% cold ethanol and vacuum-dried at 40-50C for 8 hours to obtain 30-31 g of product. Yield 90-92%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In pyridine; dichloromethane; toluene; | EXAMPLE 2 6-O-Palmitoyl-2-O-(isopropyloxycarbonyl)-L-ascorbic Acid 45 ml (0.045 mol) of a 1 M solution of isopropyl chloroformate in toluene were added dropwise at -15 C. to 17.8 g (0.042 mol) of 6-O-palmitoyl-L-ascorbic acid in 100 ml (1.24 mol) of pyridine. The reaction mixture was stirred at room temperature for a further hour and the deposited pyridinium hydrochloride was filtered off. The yellow filtrate was concentrated in vacuo with repeated codistillation with toluene. The brown oily residue was taken up in dichloromethane/toluene (1:1) and washed twice with 1 M HCl solution. Drying of the organic phase over Na2SO4 and concentration in vacuo yielded a dark yellow to brown solid, which, in divided form after suspending twice in a little cold ethyl acetate, was filtered as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
butylated hydroxytoluene (BHT) tert-butylhydroquinone (TBHQ) Ethoxyquin ascorbic acid ascorbic palmitate | ||
Representative examples of preservatives include the following: benzoic acids, esters and salts formaldehyde sodium acetate ascorbyl palmitate 1,2-benzisothiazolin-3-one (Proxel) 1,3-butylene glycol dimethylacrylate methyl p-hydroxybenzoate sodium 0-phenylphenate ethoxyquin |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
b) a mixture consisting of 9 g of decanol, 1.0 g of dodecanol added with 1% ascorbyl palmitate, butyric acid (2.0 g), phenylethyl alcohol (6.0 g) is prepared; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With procetonato-copper(II); In ethanol; ethyl acetate;Conversion of starting material; | Examples:Gel times in comparison to halonium salt based ternary redox systemsPreparation of solution 1: At room temperature in a 100 ml round bottom flask 0.083 g of procetonato-Copper(II) were dissolved in an appropriate amount of ethyl acetate. 9.917 g of Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane were added and after a brief homogenization the solvent was removed under vacuo (0.01 mbar) at 50 C. The amount of procetonato-copper(II) is adjusted so that there are 0.25 %-mol of procetonato-copper(II) within the complete resulting mixture of procetonato-copper(II) together with the reducing agent (see below: preparation of Solution 2) and the iodonium salt (see below: preparation of Solution 3).Preparation of solution 2: As described above for procetonato-copper(II) (see above: preparation of solution 1) as respective reducing agents benzoin (solvent ethyl acetate, Solution 2a) and ascorbyl palmitate (solvent ethanol, Solution 2b) are dissolved within bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the reducing agent within the complete resulting mixture of the reducing agent together with procetonato-copper(II) (see above: preparation of solution 1) and the iodonium salt (see below preparation of solution 3).Preparation of solution 3: As described above for the reducing agents (see above: preparation of solution 2) as respective iodonium salts (4-cumyl)-(4-tolyl)-iodonium tetrakis(pentafluorophenyl)borate (solvent ethyl acetate, solution 3a), (4-ocytyloxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethyl acetate, solution 3b), (4-methoxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethanol, solution 3c), [3-(2-hydroxy-tetradecyloxy)-phenyl]-phenyl-iodonium hexafluorostibonate (solvent ethanol, Solution 3d) and bis(4-tert-butylphenyl)-iodonium trifluoromethansulfonate (solvent ethanol, solution 3e) were dissolved in bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the iodonium salt within the complete resulting mixture of the iodonium salt together with procetonato-copper(II) (see above: preparation of solution 1) and the reducing agent (see above: preparation of solution 2).Preparation of Solution 4: As described above for procetonato-copper(II) (see above: preparation of solution 1) but without added solvent, a Pt(0) complex was dissolved in Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that the resulting mixture contained 500 ppm of platinum metal of the Pt(0) complex together with the iodonium salt (see above preparation of solution 3). The Pt(0) complex was prepared from hexachloroplatinum acid by reduction with 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane in the presence of a vinyl terminated poly(dimethylsiloxane) containing 1.3 %-weight of platinum metal as described e.g. within U.S. Pat Nos. 3,715,334, 3,775,352 and 3,814,730 for similar platinum complexes. Preparation of the example mixtures:i. Example mixtures with a ternary initiator system: First 1.00 g of Solution 3 was added to 1.00 g of Solution 1. Then 1.00 g of Solution 2 was added. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene.ii. Example mixture with a binary initiator system: 1.00 g of solution 4 was added to 1.00 g of Solution 3. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With procetonato-copper(II); In ethanol; ethyl acetate;Conversion of starting material; | Examples:Gel times in comparison to halonium salt based ternary redox systemsPreparation of solution 1: At room temperature in a 100 ml round bottom flask 0.083 g of procetonato-Copper(II) were dissolved in an appropriate amount of ethyl acetate. 9.917 g of Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane were added and after a brief homogenization the solvent was removed under vacuo (0.01 mbar) at 50 C. The amount of procetonato-copper(II) is adjusted so that there are 0.25 %-mol of procetonato-copper(II) within the complete resulting mixture of procetonato-copper(II) together with the reducing agent (see below: preparation of Solution 2) and the iodonium salt (see below: preparation of Solution 3).Preparation of solution 2: As described above for procetonato-copper(II) (see above: preparation of solution 1) as respective reducing agents benzoin (solvent ethyl acetate, Solution 2a) and ascorbyl palmitate (solvent ethanol, Solution 2b) are dissolved within bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the reducing agent within the complete resulting mixture of the reducing agent together with procetonato-copper(II) (see above: preparation of solution 1) and the iodonium salt (see below preparation of solution 3).Preparation of solution 3: As described above for the reducing agents (see above: preparation of solution 2) as respective iodonium salts (4-cumyl)-(4-tolyl)-iodonium tetrakis(pentafluorophenyl)borate (solvent ethyl acetate, solution 3a), (4-ocytyloxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethyl acetate, solution 3b), (4-methoxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethanol, solution 3c), [3-(2-hydroxy-tetradecyloxy)-phenyl]-phenyl-iodonium hexafluorostibonate (solvent ethanol, Solution 3d) and bis(4-tert-butylphenyl)-iodonium trifluoromethansulfonate (solvent ethanol, solution 3e) were dissolved in bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the iodonium salt within the complete resulting mixture of the iodonium salt together with procetonato-copper(II) (see above: preparation of solution 1) and the reducing agent (see above: preparation of solution 2).Preparation of Solution 4: As described above for procetonato-copper(II) (see above: preparation of solution 1) but without added solvent, a Pt(0) complex was dissolved in Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that the resulting mixture contained 500 ppm of platinum metal of the Pt(0) complex together with the iodonium salt (see above preparation of solution 3). The Pt(0) complex was prepared from hexachloroplatinum acid by reduction with 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane in the presence of a vinyl terminated poly(dimethylsiloxane) containing 1.3 %-weight of platinum metal as described e.g. within U.S. Pat Nos. 3,715,334, 3,775,352 and 3,814,730 for similar platinum complexes. Preparation of the example mixtures:i. Example mixtures with a ternary initiator system: First 1.00 g of Solution 3 was added to 1.00 g of Solution 1. Then 1.00 g of Solution 2 was added. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene.ii. Example mixture with a binary initiator system: 1.00 g of solution 4 was added to 1.00 g of Solution 3. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With procetonato-copper(II); In ethanol; ethyl acetate;Conversion of starting material; | Examples:Gel times in comparison to halonium salt based ternary redox systemsPreparation of solution 1: At room temperature in a 100 ml round bottom flask 0.083 g of procetonato-Copper(II) were dissolved in an appropriate amount of ethyl acetate. 9.917 g of Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane were added and after a brief homogenization the solvent was removed under vacuo (0.01 mbar) at 50 C. The amount of procetonato-copper(II) is adjusted so that there are 0.25 %-mol of procetonato-copper(II) within the complete resulting mixture of procetonato-copper(II) together with the reducing agent (see below: preparation of Solution 2) and the iodonium salt (see below: preparation of Solution 3).Preparation of solution 2: As described above for procetonato-copper(II) (see above: preparation of solution 1) as respective reducing agents benzoin (solvent ethyl acetate, Solution 2a) and ascorbyl palmitate (solvent ethanol, Solution 2b) are dissolved within bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the reducing agent within the complete resulting mixture of the reducing agent together with procetonato-copper(II) (see above: preparation of solution 1) and the iodonium salt (see below preparation of solution 3).Preparation of solution 3: As described above for the reducing agents (see above: preparation of solution 2) as respective iodonium salts (4-cumyl)-(4-tolyl)-iodonium tetrakis(pentafluorophenyl)borate (solvent ethyl acetate, solution 3a), (4-ocytyloxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethyl acetate, solution 3b), (4-methoxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethanol, solution 3c), [3-(2-hydroxy-tetradecyloxy)-phenyl]-phenyl-iodonium hexafluorostibonate (solvent ethanol, Solution 3d) and bis(4-tert-butylphenyl)-iodonium trifluoromethansulfonate (solvent ethanol, solution 3e) were dissolved in bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the iodonium salt within the complete resulting mixture of the iodonium salt together with procetonato-copper(II) (see above: preparation of solution 1) and the reducing agent (see above: preparation of solution 2).Preparation of Solution 4: As described above for procetonato-copper(II) (see above: preparation of solution 1) but without added solvent, a Pt(0) complex was dissolved in Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that the resulting mixture contained 500 ppm of platinum metal of the Pt(0) complex together with the iodonium salt (see above preparation of solution 3). The Pt(0) complex was prepared from hexachloroplatinum acid by reduction with 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane in the presence of a vinyl terminated poly(dimethylsiloxane) containing 1.3 %-weight of platinum metal as described e.g. within U.S. Pat Nos. 3,715,334, 3,775,352 and 3,814,730 for similar platinum complexes. Preparation of the example mixtures:i. Example mixtures with a ternary initiator system: First 1.00 g of Solution 3 was added to 1.00 g of Solution 1. Then 1.00 g of Solution 2 was added. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene.ii. Example mixture with a binary initiator system: 1.00 g of solution 4 was added to 1.00 g of Solution 3. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With procetonato-copper(II); In ethanol; ethyl acetate;Conversion of starting material; | Examples:Gel times in comparison to halonium salt based ternary redox systemsPreparation of solution 1: At room temperature in a 100 ml round bottom flask 0.083 g of procetonato-Copper(II) were dissolved in an appropriate amount of ethyl acetate. 9.917 g of Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane were added and after a brief homogenization the solvent was removed under vacuo (0.01 mbar) at 50 C. The amount of procetonato-copper(II) is adjusted so that there are 0.25 %-mol of procetonato-copper(II) within the complete resulting mixture of procetonato-copper(II) together with the reducing agent (see below: preparation of Solution 2) and the iodonium salt (see below: preparation of Solution 3).Preparation of solution 2: As described above for procetonato-copper(II) (see above: preparation of solution 1) as respective reducing agents benzoin (solvent ethyl acetate, Solution 2a) and ascorbyl palmitate (solvent ethanol, Solution 2b) are dissolved within bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the reducing agent within the complete resulting mixture of the reducing agent together with procetonato-copper(II) (see above: preparation of solution 1) and the iodonium salt (see below preparation of solution 3).Preparation of solution 3: As described above for the reducing agents (see above: preparation of solution 2) as respective iodonium salts (4-cumyl)-(4-tolyl)-iodonium tetrakis(pentafluorophenyl)borate (solvent ethyl acetate, solution 3a), (4-ocytyloxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethyl acetate, solution 3b), (4-methoxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethanol, solution 3c), [3-(2-hydroxy-tetradecyloxy)-phenyl]-phenyl-iodonium hexafluorostibonate (solvent ethanol, Solution 3d) and bis(4-tert-butylphenyl)-iodonium trifluoromethansulfonate (solvent ethanol, solution 3e) were dissolved in bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the iodonium salt within the complete resulting mixture of the iodonium salt together with procetonato-copper(II) (see above: preparation of solution 1) and the reducing agent (see above: preparation of solution 2).Preparation of Solution 4: As described above for procetonato-copper(II) (see above: preparation of solution 1) but without added solvent, a Pt(0) complex was dissolved in Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that the resulting mixture contained 500 ppm of platinum metal of the Pt(0) complex together with the iodonium salt (see above preparation of solution 3). The Pt(0) complex was prepared from hexachloroplatinum acid by reduction with 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane in the presence of a vinyl terminated poly(dimethylsiloxane) containing 1.3 %-weight of platinum metal as described e.g. within U.S. Pat Nos. 3,715,334, 3,775,352 and 3,814,730 for similar platinum complexes. Preparation of the example mixtures:i. Example mixtures with a ternary initiator system: First 1.00 g of Solution 3 was added to 1.00 g of Solution 1. Then 1.00 g of Solution 2 was added. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene.ii. Example mixture with a binary initiator system: 1.00 g of solution 4 was added to 1.00 g of Solution 3. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With procetonato-copper(II); In ethanol; ethyl acetate;Conversion of starting material; | Examples:Gel times in comparison to halonium salt based ternary redox systemsPreparation of solution 1: At room temperature in a 100 ml round bottom flask 0.083 g of procetonato-Copper(II) were dissolved in an appropriate amount of ethyl acetate. 9.917 g of Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane were added and after a brief homogenization the solvent was removed under vacuo (0.01 mbar) at 50 C. The amount of procetonato-copper(II) is adjusted so that there are 0.25 %-mol of procetonato-copper(II) within the complete resulting mixture of procetonato-copper(II) together with the reducing agent (see below: preparation of Solution 2) and the iodonium salt (see below: preparation of Solution 3).Preparation of solution 2: As described above for procetonato-copper(II) (see above: preparation of solution 1) as respective reducing agents benzoin (solvent ethyl acetate, Solution 2a) and ascorbyl palmitate (solvent ethanol, Solution 2b) are dissolved within bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the reducing agent within the complete resulting mixture of the reducing agent together with procetonato-copper(II) (see above: preparation of solution 1) and the iodonium salt (see below preparation of solution 3).Preparation of solution 3: As described above for the reducing agents (see above: preparation of solution 2) as respective iodonium salts (4-cumyl)-(4-tolyl)-iodonium tetrakis(pentafluorophenyl)borate (solvent ethyl acetate, solution 3a), (4-ocytyloxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethyl acetate, solution 3b), (4-methoxy-phenyl)-phenyl-iodonium hexafluorostibonate (solvent ethanol, solution 3c), [3-(2-hydroxy-tetradecyloxy)-phenyl]-phenyl-iodonium hexafluorostibonate (solvent ethanol, Solution 3d) and bis(4-tert-butylphenyl)-iodonium trifluoromethansulfonate (solvent ethanol, solution 3e) were dissolved in bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that there is 1.00 %-mol of the iodonium salt within the complete resulting mixture of the iodonium salt together with procetonato-copper(II) (see above: preparation of solution 1) and the reducing agent (see above: preparation of solution 2).Preparation of Solution 4: As described above for procetonato-copper(II) (see above: preparation of solution 1) but without added solvent, a Pt(0) complex was dissolved in Bis[2-(3,4-epoxycyclohexyl)-ethyl]-methyl-phenyl-silane so that the resulting mixture contained 500 ppm of platinum metal of the Pt(0) complex together with the iodonium salt (see above preparation of solution 3). The Pt(0) complex was prepared from hexachloroplatinum acid by reduction with 1,1,3,3-Tetramethyl-1,3-divinyldisiloxane in the presence of a vinyl terminated poly(dimethylsiloxane) containing 1.3 %-weight of platinum metal as described e.g. within U.S. Pat Nos. 3,715,334, 3,775,352 and 3,814,730 for similar platinum complexes. Preparation of the example mixtures:i. Example mixtures with a ternary initiator system: First 1.00 g of Solution 3 was added to 1.00 g of Solution 1. Then 1.00 g of Solution 2 was added. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene.ii. Example mixture with a binary initiator system: 1.00 g of solution 4 was added to 1.00 g of Solution 3. The resulting mixture was then homogenized by vigorously stirring by hand with a spatula made of polyethylene. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Example 8: Preparation of L-6-palmitoyl-2-alpha-lipoyl-ascorbic acid; 5.0 g of alpha-lipoic acid and 3.18 g of triethylamine were dissolved in 80 ml of methylene chloride. The reaction mixture was cooled to about -15C and then <n="23"/>3.16 g of ethyl chloroformate was gradually added thereto. The reaction mixture was stirred for 1 hour while the temperature was maintained and then further stirred at room temperature for 1 hour. The reaction mixture was cooled again to about -150C . A solution of 12.05 g of L-6-palmitoyl-ascorbic acid and 3.18 g of triethylamine in 100 ml of methylene chloride was rapidly added to the reaction mixture, which was then stirred for 2 hours while gradually increasing the temperature to room temperature. The resultant was concentrated under reduced pressure. 100 ml of a mixed solvent of n-hexane and methylene chloride (2:1 , v/v) was added to the obtained obtained oily residue. The reaction mixture was cooled to -50C and then filtered. The obtained crystal was dried to obtain 10.37 g of L-6-palmitoyl-2-alpha-lipoyl-ascorbic acid (yield: 71%). m.p.: 129-1320C1H NMR (400MHz, CDCI3), 4.89 (1H, s), 4.42-4.38(1 H, q), 4.36-4.22 (2H, m), 3.62-3.55(1 H, m), 3.23-3.10(2H, m), 2.65-2.61 (2H, t), 2.52-2.44(1 H1 m), 2.39-2.35(2H, t), 1.97-1.89(1 H, m), 1.79-1.43(8H1 m), 1.35-1.04(24H1 m), 0.90-0.88(3H, t) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With sodium hydroxide; In water; at 20℃;pH 10.0;Inert atmosphere; | General procedure: 6-O-Palmitoyl l-ascorbic acid (82.3 mg (0.20 mmol) was charged in a three neck round bottom flask of 100 mL, in 10 mL of deionized, degassed water and sonicated for 2 h to induce dissolution. In a separate a three neck round bottom flask of 100 mL, 58.9 mg (0.20 mmol) of Cp2MoCl2 in 6 mL of deionized, degassed water was also sonicated for 2 h. To this solution, the 6-O-palmitoyl-l-ascorbic acid was added and the pH adjusted to 10 with 0.1 M NaOH. The reaction mixture was stirred overnight at room temperature under a nitrogen atmosphere, forming a dark-yellow precipitate. The precipitate was filtered and washed with small amounts of water. The product was purified by column chromatography, using LH20 (lipophilic sephadex 20-100 mum) as solid phase and methanol as solvent. The product was dried under vacuum for 24 h. IR (KBr, cm- 1): 3116, 2960, 2915, 2850, 1734, 1614, 1470, 1261, 717. 1H NMR (D2O): 5.70 (s, 5H, Cp), 5.68 (s, 5H, Cp?), 5.25 (d, 1OH5, J = 6.8 Hz), 4.30 (d, 1H4, J = 4.2 Hz), 4.09 (dd, 2H6, J = 4.4 Hz, J = 11.4 Hz), 3.86 (pseudo dd, 1H5, J = 11.7 Hz, J = 7.9 Hz), 2.29 (t, 2H7, J = 7.4 Hz), 1.51(quintet, 2H8, J = 6.3 Hz), 1.24 (bs, 12H9-20), 0,86 (t, 3H21, J = 6.6 Hz). 13C NMR (DMSO-d6): delta (ppm): 177.5 (CO), 172.9 (CO), 139.82 (C2), 129.88 (C3), 102.71 (Cp), 102.48 (Cp?), 73.8, 68.3, 64.8, 33.5, 31.3, 29.1, 29.0, 28.9, 28.8, 28.5, 24.5, 22.1, 14.0. Anal. Calc. for Mo(C32H46O7): C, 60.18; H, 7.26. Found:C, 59.95; H, 7.15 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20%; 37% | With pyridine; In toluene; at 20℃; for 48h; | Example 45 (Synthesis of (S)-2-((R)-4-(diethylcarbamoyloxy)-3-hydroxy-5-oxo-2,5-dihydrofuran-2-yl)-2-hydroxyethyl palmitate (Compound 1-244) and (S)-2-((R)-3,4-bis(diethylcarbamoyloxy)-5-oxo-2,5-dihydrofuran-2-yl)-2-hydroxyethyl palmitate (Compound 1-246)) First, 6-O-palmitoyl-L-ascorbic acid (2.00 g, 4.82 mmol) was dissolved in pyridine (15 mL), and the resulting solution was cooled in an ice bath containing added salt. A toluene solution (5 mL) containing diethylcarbamoyl chloride (0.70 g, 5.16 mmol) was then added dropwise. The temperature of the reaction solution was then gradually raised to room temperature, and the reaction was allowed to proceed at the same temperature for two days. Subsequently, the insoluble material was removed by filtration and washed with toluene. The filtrate was then concentrated, and the residue was purified by silica gel column chromatography, yielding (S)-2-((R)-4-(diethylcarbamoyloxy)-3-hydroxy-5-oxo-2,5-dihydrofuran-2-yl)-2-hydroxyethyl palmitate (compound 1-244) in an amount of 0.50 g, a yield of 37%, and (S)-2-((R)-3,4-bis(diethylcarbamoyloxy)-5-oxo-2,5-dihydrofuran-2-yl)-2-hydroxyethyl palmitate (compound 1-246) in an amount of 0.12 g, a yield of 20%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With pyridine; In toluene; at 20℃;Cooling with ice; | Example 50 (Synthesis of (S)-2-hydroxy-2-((R)-3-hydroxy-5-oxo-4-(tosyloxy)-2,5-dihydrofuran-2-yl)ethyl palmitate (Compound 1-249)) First, 6-O-palmitoyl-L-ascorbic acid (2.00 g, 4.82 mmol) was dissolved in pyridine (15 mL), and the resulting solution was cooled in an ice bath containing added salt. A toluene solution (5 mL) containing tosyl chloride (0.98 g, 5.14 mmol) was then added dropwise. The temperature of the reaction solution was then gradually raised to room temperature, and the reaction was allowed to proceed overnight at the same temperature. Subsequently, the insoluble material was removed by filtration and washed with toluene. The filtrate was then concentrated, and the residue was purified by silica gel column chromatography, yielding (S)-2-hydroxy-2-((R)-3-hydroxy-5-oxo-4-(tosyloxy)-2,5-dihydrofuran-2-yl)ethyl palmitate (compound 1-249) in an amount of 0.82 g, a yield of 30%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With pyridine; at 20℃;Cooling with ice; | Example 49 (Synthesis of (S)-2-((R)-4-(tert-butoxycarbonyloxy)-3-hydroxy-5-oxo-2,5-dihydrofuran-2-yl)-2-hydroxyethyl palmitate (Compound 1-247)) First, 6-O-palmitoyl-L-ascorbic acid (2.00 g, 4.82 mmol) was dissolved in pyridine (15 mL), and the resulting solution was cooled in an ice bath containing added salt. A toluene solution (5 mL) containing BoC2O (1.13 g, 5.18 mmol) was then added dropwise. The temperature of the reaction solution was then gradually raised to room temperature, and the reaction was allowed to proceed overnight at the same temperature. Subsequently, the insoluble material was removed by filtration and washed with toluene. The filtrate was then concentrated, and the residue was purified by silica gel column chromatography, yielding (S)-2-((R)-4-(tert-butoxycarbonyloxy)-3-hydroxy-5-oxo-2,5-dihydrofuran-2-yl)-2-hydroxyethyl palmitate (compound 1-247) in an amount of 1.00 g, a yield of 40%. |