2,2-bis(hydroxymethyl)propane-1,3-diol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:220.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suitable reactor are introduced 500 parts of WW rosin which is then heated under nitrogen to 220° C. Thereafter, 67.5 parts of technical pentaerythritol (PE) are added. The temperature is next raised to between 270° C. and 275° C., and stirred for one hour, at which time the acid number is found to be equal to 103. A catalyst, namely, 0.25 part of p-touenesulfonic acid is then added to the reaction mixture. The reaction temperature is maintained for a total of 11 hours at 275° C. At the end of this period, esterification had been found to be substantially completed, producing a rosin/PE ester having an acid number equal to 13, an N color, and an 84° C. Ring and Ball softening point. The temperature is next raised to between 270° C. and 275° C. A catalyst, namely, 0.25 part of p-touenesulfonic acid is then added to the reaction mixture The reaction temperature is maintained for a total of 11 hours at 275° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Pentaerythrityl tetrasulfate ammonium salt is prepared from pentaerythritol and sulfamic acid in N,N,-dimethylformamide. A mixture of 5 grams of pyrrole and 5 grams of the ammonium salt in 200 ml. water is prepared and electropolymerized in a 8×7×4.5 cm reaction vessel wherein the cathode is a 15×5×0.025 cm nickel sheet. About 40 cm2 of the nickel sheet is immersed in the bath. The distance between electrodes is 4.5 centimeters. Electropolymerization is conducted at a current of 0.3 amperes for a period of 10 minutes yielding a black electronically conducting film characterized by a somewhat rough surface on the solution side of the film. electropolymerized in a 8×7×4.5 cm reaction vessel wherein the cathode of 10 minutes yielding a black

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Pentaerythritol (50 g, 0.36 mol) and p-toluenesulfonic acid monohydrate (0.61 g) were dissolved in 500 ml N,N-dimethylformamide (DMF, dried by molecular sieve at room temperature) at about 80° C., and then the mixture was allowed to cool undisturbed. When the solution cooled to about 40° C., stirring was started and 55.4 ml 2,2-dimethoxypropane (0.36 mol) was added. After 24 hours of stirring at room temperature, the solution was stirred at room temperature with 9.0 g of base treated DOWEX 1XZ-100 ion-exchange resin for 1 hour, filtered and then the solvent was evaporated under reduced pressure at 85° C. The base treated DOWEX 1XZ-100 ion exchange was prepared by washing 30 g. twice with 200 ml of deionized water, then washed with 300 ml of 4% aq. NaOH and then washed three times with 200 ml of water, filtered and then air-dried in a hood. After the treatment with this resin as noted above, the dry product was ground and extracted (Soxhlet), first with light petroleum ether (b.p. 40-60° C.) for 6 hours, then with diethyl ether for 12 hours, collected and dried. Yield: White crystals (40.0 g, 61.9%). M.P. 124.5°-125.5° C.; 11H-NMR (300 MHz, DMSO-d6) 1.28 ppm (s, 6H), 3.34 ppm (d, J=5.7 Hz, 4H), 3.58 ppm (s, 4H), 4.47 ppm (t, J=5.4 Hz, 2H); to cool undisturbed After 24 hours of stirring at room temperature treated DOWEX 1XZ-100 ion-exchange resin for 1 hour filtered the solvent was evaporated under reduced pressure at 85° C The base treated DOWEX 1XZ-100 ion exchange was prepared by washing 30 g twice with 200 ml of deionized water, then washed with 300 ml of 4% aq. NaOH washed three times with 200 ml of water filtered air-dried in a hood extracted (Soxhlet) with diethyl ether for 12 hours collected dried

Conditions: temp:170.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a flask equipped with a stirrer, a distilling column, a nitrogen inlet, a heating jacket, and a thermometer were charged 486 g of triethyl orthoacetate, 408 g of pentaerythritol, 300 g of diethylene glycol dimethyl ether, and 0.9 g of PTSA. The mixture was gradually heated to 170° C. over a period of 5 hours. During this time 490 g of distillate were obtained. The distillate contained mostly ethanol and small amounts of diethylene glycol dimethyl ether. The temperature was lowered to 100° C., and the remaining diethylene glycol dimethyl ether was distilled off under reduced pressure (30 mbar). The residue was subjected to vacuum distillation. The fraction having a boiling temperature of 126-130° C. at a pressure of 4 mbar yielded 426 g of oil. This oil solidified to a clear solid having a melting point of 99° C. and had the following structure Into a flask equipped with a stirrer During this time 490 g of distillate were obtained was lowered to 100° C. the remaining diethylene glycol dimethyl ether was distilled off under reduced pressure (30 mbar) The residue was subjected to vacuum distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 2 liter, three-necked flask equipped with a reflux condenser and an addition funnel are placed 200 g pentaerythritol (1.47 mole) and 16 ml 48% hydrobromic acid in about 500 ml glacial acetic acid. The mixture is refluxed for about one-half hour until all pentaerythritol is dissolved. Then, 170 ml 48% hydrobromic acid are added, followed by 310 ml acetic anhydride and the mixture is refluxed for 3 hours. Then, 94 ml 48% hydrobromic acid followed by 150 ml acetic anhydride are added and the mixture is refluxed for an additional 3 hours. The acetic acid is then removed as completely as possible on a rotary evaporator. Ethanol (95%, 750 ml) and 17 ml 48% hydrobromic acid are then added to the residue. The flask is equipped with 1 m Vigreux column and the azeotrope ethyl acetate/ethanol is slowly distilled off. When 500 ml distillate has been collected, an additional 750 ml 95% ethanol is added and the distillation is continued until about 400 ml is left over. After cooling, the precipitated pentaerythritol is filtered off. The solvent is evaporated and the residue is dissolved in water. The aqueous phase is extracted twice with carbon tetrachloride and twice with ether. The water is evaporated on the rotary evaporator and the last traces of water are removed by azeotropic distillation with toluene using a Dean-Stark trap. The solid is recrystallized from chloroform containing 10% acetonitrile. The first crop yielded 190 g monobromopentaerythritol. The total yield is 70%. In a 2 liter, three-necked flask equipped with a reflux condenser and an addition funnel is dissolved the mixture is refluxed for 3 hours are added the mixture is refluxed for an additional 3 hours The acetic acid is then removed as completely as possible on a rotary evaporator Ethanol (95%, 750 ml) and 17 ml 48% hydrobromic acid are then added to the residue The flask is equipped with 1 m Vigreux column the azeotrope ethyl acetate/ethanol is slowly distilled off When 500 ml distillate has been collected an additional 750 ml 95% ethanol is added the distillation is left over After cooling the precipitated pentaerythritol is filtered off The solvent is evaporated the residue is dissolved in water The aqueous phase is extracted twice with carbon tetrachloride and twice with ether The water is evaporated on the rotary evaporator the last traces of water are removed by azeotropic distillation with toluene using a Dean-Stark trap The solid is recrystallized from chloroform containing 10% acetonitrile

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 2 liter, three-necked flask equipped with a reflux condenser and an addition funnel are placed 200 g pentaerythritol (1.47 mole) and 16 ml 48% hydrobromic acid in about 500 ml glacial acetic acid. The mixture is refluxed for about one-half hour until all pentaerythritol is dissolved. Then 170 ml 48% hydrobromic acid are added, followed by 310 ml acetic anhydride and the mixture is refluxed for 3 hours. Then, 94 ml 48% hydrobromic acid followed by 150 ml acetic anhydride are added and the mixture is refluxed for an additional 3 hours. The acetic acid is then removed as completely as possible on a rotary evaporator. Ethanol (95%, 750 ml) and 17 ml 48% hydrobromic acid are then added to the residue. The flask is equipped with 1 m Vigreux column and the azeotrope ethyl acetate/ethanol is slowly distilled off. When 500 ml distillate has been collected, an additional 750 ml 95% ethanol is added and the distillation is continued until about 400 ml is left over. After cooling, the precipitated pentaerythritol is filtered off. The solvent is evaporated and the residue is dissolved in water. The aqueous phase is extracted twice with carbon tetrachloride and twice with ether. The water is evaporated on the rotary evaporator and the last traces of water are removed by azeotropic distillation with toluene using a Dean-Stark trap. The solid is recrystalized from chloroform containing 10% acetonitrile. The first crop yielded 190 g monobromopentaerythritol. The total yield is 70%. In a 2 liter, three-necked flask equipped with a reflux condenser and an addition funnel is dissolved the mixture is refluxed for 3 hours are added the mixture is refluxed for an additional 3 hours The acetic acid is then removed as completely as possible on a rotary evaporator Ethanol (95%, 750 ml) and 17 ml 48% hydrobromic acid are then added to the residue The flask is equipped with 1 m Vigreux column the azeotrope ethyl acetate/ethanol is slowly distilled off When 500 ml distillate has been collected an additional 750 ml 95% ethanol is added the distillation is left over After cooling the precipitated pentaerythritol is filtered off The solvent is evaporated the residue is dissolved in water The aqueous phase is extracted twice with carbon tetrachloride and twice with ether The water is evaporated on the rotary evaporator the last traces of water are removed by azeotropic distillation with toluene using a Dean-Stark trap The solid is recrystalized from chloroform containing 10% acetonitrile

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 0.5 mol of propenyl 4-trifluoromethylphenyl ether, 0.25 mol of pentaerythritol and 5 g of p-toluenesulphonic acid in 500 ml of carbon tetrachloride was stirred and refluxed under nitrogen for 40 minutes. The resulting solution was washed with 250 ml of water, and then dried by azeotroping 150 ml solvent in vacuo. After addition of 150 ml of fresh carbon tetrachloride, chlorine was passed into the solution for 2 hours, after which the solution was washed with 250 ml of water and the solvent was evaporated. The remaining product was purified by fractional distillation to give 74.8 g of 2chloro-4-trifluoromethylphenol, b.p: 52°-53.5° C. at 6 Torr., which was identified and shown by gas chromatography to have a purity of greater than 97%. refluxed under nitrogen for 40 minutes The resulting solution was washed with 250 ml of water dried by azeotroping 150 ml solvent in vacuo After addition of 150 ml of fresh carbon tetrachloride, chlorine after which the solution was washed with 250 ml of water the solvent was evaporated The remaining product was purified by fractional distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500-milliliter round-bottom flask equipped with a magnetic stirring bar, a water separator, and a condenser were added 27.23 grams (0.200 mol) of pentaerythritol, 90.22 grams (0.850 mol) of 2-mercaptopropionic acid, 100 milliliters of toluene, and 0.5 milliliter of concentrated sulfuric acid. The mixture was heated under reflux with stirring. After about 2 days, the solid material had disappeared, and about 17 milliliters (0.94 mol) of water had been collected by the water separator. Upon cooling to room temperature, the mixture was extracted with 30 milliliters of saturated NaHCO3 solution and washed with two 50-milliliter portions of water. The organic layer was dried over anhydrous MgSO4, and most of the toluene and residual 2-mercaptopropionic acid were removed by distillation under vacuum. Recrystallization of the residue from ethanol gave 86.0 grams (88.4%, calcd. 97.3 grams) of pentaerythritol tetrakis(2-mercaptopropionate) as a white solid, mp 93-96° C.; 1H NMR (in CDCl3 w/TMS, ppm): 4.17-4.30 (AB m, 8H, CH2O), 3.50 (pentuplet, 4H, CHSH), 2.17 (d of d, 4H, SH), 1.51 (d, 12H, CH3); {1H}13C NMR (in CDCl3 w/TMS, ppm): 172.79 (C═O), 62.47 (CH2O), 43.05 [C(CH2)4], 35.43 (CHSH), 20.94 (CH3). To a 500-milliliter round-bottom flask equipped with a magnetic stirring bar The mixture was heated under reflux the mixture was extracted with 30 milliliters of saturated NaHCO3 solution washed with two 50-milliliter portions of water The organic layer was dried over anhydrous MgSO4 most of the toluene and residual 2-mercaptopropionic acid were removed by distillation under vacuum Recrystallization of the residue from ethanol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,2-bis(hydroxymethyl)propane-1,3-diol (10.55 g, 77 mmole) was taken up in dry pyridine (100 mL). Tert-butyldiphenylsilyl chloride (4.26 g, 15 mmole, 0.2 eq) was then added dropwise over 10 minutes to the pyridine solution at ambient temperature. The reaction mixture was stirred at ambient temperature for 24 hours. TLC (EtOAc) indicated that the reaction was complete. The reaction was diluted with EtOAc (250 mL), washed with 10% HCl (3×200 mL). The organic layer was dried over sodium sulfate and then concentrated in vacuo to afford a thick pale yellow oil. Column chromatography on silica gel (200 g), eluted with EtOAC followed by concentration of the appropriate fractions gave 5.01 g of the title compound as a clear colorless oil which solidified very slowly upon standing (86%). 1H NMR (300 MHz, CDCl3) δ 7.65 (m, 4H), 7.42 (m, 6H), 3.74 (s, 6H), 3.66 (s, 2H), 1.08 (s, 9H); MS (70 eV, EI) 392 (M+NH4)+. washed with 10% HCl (3×200 mL) The organic layer was dried over sodium sulfate concentrated in vacuo to afford a thick pale yellow oil Column chromatography on silica gel (200 g), eluted with EtOAC

Conditions: temp:135.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A Bis-(3-n-decylthiopropionoxy) Bis-(3-n-octylthiopropionoxy) neopentane was prepared. 150 grams (0.609 mol) of 3-n-decylthiopropionic acid and 132.9 grams (0.609 mol) of 3-n-octylthiopropionic acid were mixed, rendered molten and stirred within a reaction vessel, to which 39.5 grams (0.290 mol) of pentaerythritol were added, followed by 4.4 grams (0.023 mol) of para-toluenesulfonic acid catalyst. A vacuum of 40 torr was applied, and the mixture was heated to 135° C. Heating was continued for five hours, after which a liquid product having an acid value of 11.4 was obtained. This product was washed with 500 ml. of hot 3% sodium sulfate and then vacuum stripped It was washed with six 300 ml. aliquots of hot methanol, after which the acid value was 0.4. The yield was 250.9 grams, or 87.1 percent A comparison of the actual product distribution versus the statistical distribution can be summarized as follows: were added Heating was obtained This product was washed with 500 ml was washed with six 300 ml

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,2-bis(hydroxymethyl)propane-1,3-diol (10.55 g, 77 mmole) was taken up in dry pyridine (100 mL). Tert-butyldiphenylsilyl chloride (4.26 g, 15 mmole, 0.2 eq) was then added dropwise over 10 minutes to the pyridine solution at ambient temperature. The reaction mixture was stirred at ambient temperature for 24 hours. TLC (EtOAc) indicated that the reaction was complete. The reaction was diluted with EtOAc (250 mL), washed with 10% HCl (3×200 mL). The organic layer was dried over sodium sulfate and then concentrated in vacuo to afford a thick pale yellow oil. Column chromatography on silica gel (200 g), eluted with EtOAC followed by concentration of the appropriate fractions gave 5.01 g of the title compound as a clear colorless oil which solidified very slowly upon standing (86%). 1H NMR (300 MHz, CDCl3) 7.65 (m, 4H), 7.42 (m, 6H), 3.74 (s, 6H), 3.66 (s, 2H), 1.08 (s, 9H); MS (70 eV, EI) 392 (M+NH4)+. washed with 10% HCl (3×200 mL) The organic layer was dried over sodium sulfate concentrated in vacuo to afford a thick pale yellow oil Column chromatography on silica gel (200 g), eluted with EtOAC