Structure of 102-62-5
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| CAS No. : | 102-62-5 |
| Formula : | C7H12O5 |
| M.W : | 176.17 |
| SMILES Code : | OCC(OC(C)=O)COC(C)=O |
| English Name : | 3-Hydroxypropane-1,2-diyl diacetate |
| MDL No. : | MFCD00040498 |
| InChI Key : | UXDDRFCJKNROTO-UHFFFAOYSA-N |
| Pubchem ID : | 66021 |
* 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 |
|---|---|---|
| at 120℃; for 3h; | ||
| With mesoporous niobium-silicate at 423℃; for 4h; Inert atmosphere; neat (no solvent); | ||
| With mesoporous niobiosilicate material MP-MCF* at 149.84℃; for 4h; Inert atmosphere; |
| With graphene oxide at 120℃; for 1h; Autoclave; | 2.3. Catalytic reaction The catalytic tests for glycerol esterification with acetic acid were carried out in a stainless steel autoclave with a magnetic stirring. Typically, 2.0 g glycerol and 13.0 g acetic acid with 0.1 g GO were added into the reactor and then the mixture was heated to the desired temperature for a specified time. Reaction conditions were changed to investigate the dependence of main variables such as time, reaction temperature, catalyst loading and molar ratio of acetic acid/glycerol.When the reaction was terminated, the reactor was cooled in an ice-water bath. After the mixture was separated by centrifugation, the obtained products were diluted with ethanol and analyzed by GC with a FID using a DB-1 capillary column. Corrected area normalization method was used to quantify the products. The assignments of these products were also determined by GC-MS. | |
| With Amberlyst-70 In toluene at 20℃; for 24h; | ||
| at 115℃; for 10h; | ||
| With pyridinium propyl sulfobetaine-immobilized tungstophosphoric acid at 105℃; for 6h; Dean-Stark; Inert atmosphere; | 2.3. Catalytic acetylation reaction Acetylation of glycerol (GL) over the PPS-TPA-HOAc catalystwas carried out as follows: first, known amounts of GL and HOAcreactants were added into the reaction flask containing the liquidPPS-TPA-HOAc catalyst under ambient conditions, leading to theformation of biphasic liquid layers of reactants and catalyst, asshown in Fig. 1b. It is noted that a stoichiometric amount of HOAcwas already included as solvent in the TPA-immobilized IL catalystat the bottom layer, while the reactants reside at the upper layer.The reaction system becomes a homogeneous solution mixtureafter thorough stirring, as illustrated in Fig. 1c. The acetylationreactions were carried out at different temperatures (85-125 C)under steady stirring (ca. 400 rpm) condition and allowed to proceedcontinuously for 6 h.Since water is inevitably formed as a by-product during acetylationof GL (Scheme 1), a Dean-Stark apparatus, facilitated by formationof water-toluene azeotrope at 85 C, was exploited undernitrogen bubbling for continuous removal of water during thereaction. The reaction products may readily be extracted in a semicontinuousmanner by temporarily stopping the stirrer (say, for ca.2 min) to allow for self-separation of the biphasic (products andcatalyst) liquid layers (Fig. 1d). Subsequently, the upper organiclayer containing GMA, GDA, and GTA (see Scheme 1) may beremoved easily by suction, while the PPS-TPA-HOAc catalystresiding in the bottom layer could be recycled. The above proceduresnormally prevail for acetylation reaction carried out withhigh GL conversions. Typically, ca. 0.5 mL of the upper organicmixture was withdrawn at a reaction time interval of 1, 3, and 6 h, followed by product analysis with gas chromatography. On theother hand, for reaction with low GL conversions, an effective selfseparationof the organic products and the catalyst cannot beachieved (see Fig. 1e). In this case, an online evacuation procedure(normally performed at 60 C and under 33 Torr pressure) is inevitableto remove excessive (unreacted) HOAc. Typically, this procedurewas proceeded until the reaction system restores its biphasicliquid layers (Fig. 1f). Thus, through careful control of reaction conditionswhile continuously removing water out of the system, followedby subsequent extraction of reaction products and refillingof fresh GL and HOAc reactants, a nearly continuous cycle for conversionof GL to GTA may be achieved. Accordingly, the recyclabilityof the homogeneous PPS-TPA-HOAc catalyst may also beexamined. In addition, the effects of TPA pretreatment condition,HOAc/GL molar ratio of the feed, and reaction temperature on catalyticperformances of the PPS-TPA-HOAc catalyst during acylationreaction were also investigated. | |
| With toluene for 1h; Inert atmosphere; Dean-Stark; | 2.3. Catalytic acetylation reaction General procedure: Acetylation of glycerol (GL) over thePPS-TPA-HOAc catalyst was carried out as follows: first, known amounts of GL and HOAc reactants were added into the reaction flask containing the liquid PPS-TPA-HOAc catalyst under ambient conditions, leading to the formation of biphasic liquid layers of reactants and catalyst, as shown in Fig. 1b. It is noted that a stoichiometric amount of HOAc was already included as solvent in the TPA-immobilized IL catalyst at the bottom layer, while the reactants reside at the upper layer. The reaction system becomes a homogeneous solution mixture after thorough stirring, as illustrated in Fig. 1c. The acetylation reactions were carried out at different temperatures (85-125 °C) under steady stirring (ca. 400 rpm) condition and allowed to proceed continuously for 6 h. Since water is inevitably formed as a by-product during acetylation of GL (Scheme 1), a Dean-Stark apparatus, facilitated by formation of water-toluene azeotrope at 85 °C, was exploited under nitrogen bubbling for continuous removal of water during the reaction. The reaction products may readily be extracted in a semicontinuous manner by temporarily stopping the stirrer (say, for ca. 2 min) to allow for self-separation of the biphasic (products and catalyst) liquid layers (Fig. 1d). Subsequently, the upper organic layer containing GMA, GDA, and GTA (see Scheme 1) may be removed easily by suction, while the PPS-TPA-HOAc catalyst residing in the bottom layer could be recycled. The above procedures normally prevail for acetylation reaction carried out with high GL conversions. Typically, ca. 0.5 mL of the upper organic mixture was withdrawn at a reaction time interval of 1, 3, and 6 h, followed by product analysis with gas chromatography. On the other hand, for reaction with low GL conversions, an effective self-separation of the organic products and the catalyst cannot be achieved (see Fig. 1e). In this case, an online evacuation procedure (normally performed at 60 °C and under 33 Torr pressure) is inevitable to remove excessive (unreacted) HOAc. Typically, this procedure was proceeded until the reaction system restores its biphasic liquid layers (Fig. 1f). Thus, through careful control of reaction conditions while continuously removing water out of the system, followed by subsequent extraction of reaction products and refilling of fresh GL and HOAc reactants, a nearly continuous cycle for conversion of GL to GTA may be achieved. Accordingly, the recyclability of the homogeneous PPS-TPA-HOAc catalyst may also be examined. In addition, the effects of TPA pretreatment condition, HOAc/GL molar ratio of the feed, and reaction temperature on catalytic performances ofthe PPS-TPA-HOAc catalyst during acylation reaction were also investigated. | |
| With silicotungstic acid supported on silica In toluene at 105℃; for 4h; | ||
| With C4H5N3O2*C7H8O3S at 120℃; for 0.166667h; Schlenk technique; | ||
| With phosphomolybdic acid at 80℃; for 6h; | ||
| With Amberlyst-15 at 70℃; for 4h; | ||
| With phosphate modified silica at 120℃; | 2.2 Glycerin Acetylation Catalytic Tests The glycerin (Glyc, 99% from Fluka) acetylation with aceticacid (HAc, glacial from Fluka) was studied in a 500 mLround bottom Pyrex flask equipped with a condenser anda magnetic stirrer. The reaction temperature was kept at 120 °C using a nest shape electrical heating jacket withtemperature control, whereas the temperature sensor isimmersed in the reaction medium. The catalytic tests werecarried out in conditions selected from the literature [42]using 500 mg of catalyst (15 wt%, glycerin basis), HAc/Glyc = 9 molar ratio. After the reaction, the catalyst wasremoved by filtration and the liquid effluent was analyzedby GC using a Varian CP 3800 chromatograph equippedwith a flame ionization detector. The pure MAG, DAG,TAG, glycerin, and acetic acid were injected separately todetermine the retention time of each component for a fusedsilica capillary column (0.32 mm of internal diameter, 15 mlength with a 0.1 μm of film thickness of Methyl 5% PhenylSilicone). Chromatograms were acquired in the conditionslisted in Table 3. | |
| With 20 % (w/w) Cs2.5H0.5PW12O40/K-10 clay at 120℃; for 4h; | 2.4. Catalytic experiments and analytical methods A typical esterification experiment of glycerol with acetic acid wasconducted in a 100 mL three-neck cylindrical glass reactor, equippedwith overhead stirring, a sample port, and a reflux condenser. Thereactor was charged with glycerol (0.10 mol), acetic acid (0.90 mol),catalyst (0.01 g/cm), and diphenyl ether (DPE) as the internal standard,making the total reaction volume 50 mL. The reaction mixture wasvigorously stirred at varying temperatures, and the reaction wascontinued until maximum conversion was achieved. Analysis was performedusing gas chromatography (GC, Chemito 1000) equipped with aBPX-50 capillary column (length: 30 m, ID: 0.25 mm) and a flameionization detector (FID). Product confirmation was further validatedusing GC-MS with the same capillary column. All experiments wererepeated thrice and the average values are given in the plots of conversionversus time. The standard deviation was within ±5 %. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| at 79.84℃; for 3h; | Glycerol acetylation reaction Glycerol acetylation with acetic acid was conducted in a 500 ml three-neck round-bottom flask equipped with a reflux condenser at atmospheric pressure. All the catalysts were utilized as powders. Amberlyst-15 (Rohm & Hass) beads were crushed into powders with sizes between 125 and 180 μm. The reactor was placed in a heating mantle, and the inner temperature of the reactor was isothermally maintained by PID control. In the typical procedure, 78.2 g of acetic acid (Alfa, 99.7%) and 1.0 g of the catalyst powder were placed into the reactor at a constant temperature of 353 K, and then 20.0 g of glycerol (Alfa, HPLC grade) at the same temperature was added with stirring. The products were sampled periodically during the reaction using a micro-syringe and were analyzed with a flame ionization detector (FID) equipped gas chromatograph (Agilent 7890A). After each reaction batch, the catalyst was collected by centrifugation, washed with methanol (Amberlyst-15) or deionized water (SO3H-Cell, SO3H-DOC, SO3H-NDOC) several times, and dried in a vacuum oven at 323 K for 20 h for utilization in the subsequent reaction batch. Glycerol conversion turnover rate (TOR) to combined di- and triacetin products on SO3H-NDOC and Amberlyst-15 was obtained according to the following equation: | |
| With karanja catalyst (KJ-400) at 120℃; for 4h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sulfonic acid functionalized cellulose at 79.84℃; for 3h; | Glycerol acetylation reaction Glycerol acetylation with acetic acid was conducted in a 500 ml three-neck round-bottom flask equipped with a reflux condenser at atmospheric pressure. All the catalysts were utilized as powders. Amberlyst-15 (Rohm & Hass) beads were crushed into powders with sizes between 125 and 180 μm. The reactor was placed in a heating mantle, and the inner temperature of the reactor was isothermally maintained by PID control. In the typical procedure, 78.2 g of acetic acid (Alfa, 99.7%) and 1.0 g of the catalyst powder were placed into the reactor at a constant temperature of 353 K, and then 20.0 g of glycerol (Alfa, HPLC grade) at the same temperature was added with stirring. The products were sampled periodically during the reaction using a micro-syringe and were analyzed with a flame ionization detector (FID) equipped gas chromatograph (Agilent 7890A). After each reaction batch, the catalyst was collected by centrifugation, washed with methanol (Amberlyst-15) or deionized water (SO3H-Cell, SO3H-DOC, SO3H-NDOC) several times, and dried in a vacuum oven at 323 K for 20 h for utilization in the subsequent reaction batch. Glycerol conversion turnover rate (TOR) to combined di- and triacetin products on SO3H-NDOC and Amberlyst-15 was obtained according to the following equation: | |
| With sulfonic acid functionalized deoxycellulose at 79.84℃; for 3h; | Glycerol acetylation reaction Glycerol acetylation with acetic acid was conducted in a 500 ml three-neck round-bottom flask equipped with a reflux condenser at atmospheric pressure. All the catalysts were utilized as powders. Amberlyst-15 (Rohm & Hass) beads were crushed into powders with sizes between 125 and 180 μm. The reactor was placed in a heating mantle, and the inner temperature of the reactor was isothermally maintained by PID control. In the typical procedure, 78.2 g of acetic acid (Alfa, 99.7%) and 1.0 g of the catalyst powder were placed into the reactor at a constant temperature of 353 K, and then 20.0 g of glycerol (Alfa, HPLC grade) at the same temperature was added with stirring. The products were sampled periodically during the reaction using a micro-syringe and were analyzed with a flame ionization detector (FID) equipped gas chromatograph (Agilent 7890A). After each reaction batch, the catalyst was collected by centrifugation, washed with methanol (Amberlyst-15) or deionized water (SO3H-Cell, SO3H-DOC, SO3H-NDOC) several times, and dried in a vacuum oven at 323 K for 20 h for utilization in the subsequent reaction batch. Glycerol conversion turnover rate (TOR) to combined di- and triacetin products on SO3H-NDOC and Amberlyst-15 was obtained according to the following equation: | |
| With zirconium incorporated on three-dimensional ordered mesoporous silica at 130℃; for 10h; Dean-Stark; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With 3 percent yttrium-grafted mesostructured SBA-3 catalyst at 110℃; for 3h; | 2.5. Catalytic reactions The transesterification reaction of glycerol with methyl acetate was carried out in 50 ml round bottom glass flasks immersed in an oil bath and mounted on hot plate equipped with a magnetic stirrer. In a typical run, 4 g of anhydrous glycerol and 27.5-41.3 ml of methyl acetate at variant molar ratios of glycerol to methyl acetate were fed to the reactor, and 0.15 g of solid catalyst was added. The reaction mixture was heated to the desired reaction temperature (80-120 C) at constant stirring of 530 rpm for reaction duration of 30-180 min. After completion of the reaction, the used catalyst was separated by centrifugation and reactivated by washing it with methanol at 45 C and then air dried at 80 C for 4 h to recuperate its catalytic activity. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With di(n-butyl)tin oxide; triethylamine In dichloromethane at 5 - 20℃; for 2.5h; Inert atmosphere; Overall yield = 86 %; Overall yield = 1.48 g; | 4.10. 1,3-Diacetylglycerol (11) contaminated with (±)-1,2-diacetylglycerol [(±)-12] Triethylamine (1.01 g, 10 mmol) and (n-Bu)2SnO(2.42 g,9.7 mmol) were added to a solution of (±)-10 (1.32 g, 9.7 mmol) in dry CH2Cl2 (70 mL) under argon. The suspension was stirred for15 min at room temperature. A solution of acetyl chloride (790 mg,10.1 mmol) in dry CH2Cl2 (4 mL) was added dropwise to the stirred and ice-cooled suspension. Stirring was continued for 30 min at 5-10 °C and for 2 h at room temperature. The mixture was filtered through Celite. The Celite layer was washed with EtOAc, and the combined filtrate and washings were concentrated in vacuo. The residue (1.8 g) was chromatographed over SiO2 (25 g). Elution with hexane/EtOAc (2:1) gave 1.48 g (86%) of a 65:35 mixture of 11 and(±)-12 as a colorless oil. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With zinc(II) tetrahydroborate In tetrahydrofuran at 0 - 5℃; for 0.333333h; Overall yield = 61 %; Overall yield = 2.46 g; | 4.15. 1,3-Diacetylglycerol (11) contaminated with (±)-12 byreduction of 15 NaBH4 used in this experiment was washed thoroughly by stirring with EtOAc for 3 h at room temperature, collected on a glassfilter, washed with Et2O, and dried to remove alkaline impurities.16A solution of ZnCl2 (612 mg, 4.5 mmol) in dry THF (8 mL)was addedto a stirred and ice-cooled suspension of NaBH4 (342 mg, 9 mmol)in dry THF (12 mL). A solution of 15 (3.00 g, 17 mmol) in dry THF(10 mL) was added dropwise to the stirred and ice-cooled solution of Zn(BH4)2. Stirring was continued for 20 min at 0-5 °C. The reactionwas quenched by the addition of acetic acid (1 mL), and the mixture was concentrated in vacuo. The residue was triturated with hexane/EtOAc (3:2), and transferred on a SiO2 (25 g) column. Elution with hexane/EtOAc (3:2) gave 2.46 g (61%) of a mixture of 11and (±)-12. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 30 %Chromat. 2: 29 %Chromat. | With p-toluenesulfonic acid treated montmorillonite at 120℃; for 1h; Microwave irradiation; | |
| 1: 56 %Chromat. 2: 14 %Chromat. | With phenoldisulfonic acid treated montmorillonite at 120℃; for 1h; Microwave irradiation; | |
| 1: 41 %Chromat. 2: 9 %Chromat. | With aluminium treated montmorillonite at 120℃; for 1h; Microwave irradiation; |
| With 3O40SiW12(4-)*4Fe(3+) In water at 59.84℃; for 8h; | 2.4. Catalytic tests General procedure: Typically, a 25 mL three-necked glass flask, equipped with asampling system and a reflux condenser was charged with glycerol(ca. 46.72 mmol), different volumes of acetic acid and an adequateamount of HPA salt catalyst (ca.0.06 mmol). The reaction was per-formed using magnetic stirring at a temperature of 333 K for over2 h.The effects of main reaction parameters (i.e. reactants stoi-chiometry, temperature, catalyst concentration) were assessed.The HOAc: glycerol molar ratio was varied over four different pro-portions (i.e.3:1; 6:1; 9:1 and 12:1 respectively). Control reactionswere performed for each molar proportion in the absence of cata-lyst. The activity of the most active HPA salt to the activity of metalnitrate and heteropolyacid precursor alone was also compared. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With methanesulfonic acid treated montmorillonite at 60℃; for 1h; Microwave irradiation; | ||
| With 3Co(2+)*2PW12O40(3-) = Co3(PW12O40)2 In water at 59.84℃; for 8h; | 2.4. Catalytic tests General procedure: Typically, a 25 mL three-necked glass flask, equipped with asampling system and a reflux condenser was charged with glycerol(ca. 46.72 mmol), different volumes of acetic acid and an adequateamount of HPA salt catalyst (ca.0.06 mmol). The reaction was per-formed using magnetic stirring at a temperature of 333 K for over2 h.The effects of main reaction parameters (i.e. reactants stoi-chiometry, temperature, catalyst concentration) were assessed.The HOAc: glycerol molar ratio was varied over four different pro-portions (i.e.3:1; 6:1; 9:1 and 12:1 respectively). Control reactionswere performed for each molar proportion in the absence of cata-lyst. The activity of the most active HPA salt to the activity of metalnitrate and heteropolyacid precursor alone was also compared. | |
| With iron(III) 12-molybdophosphate In water at 59.84℃; for 8h; | 2.4. Catalytic tests General procedure: Typically, a 25 mL three-necked glass flask, equipped with asampling system and a reflux condenser was charged with glycerol(ca. 46.72 mmol), different volumes of acetic acid and an adequateamount of HPA salt catalyst (ca.0.06 mmol). The reaction was per-formed using magnetic stirring at a temperature of 333 K for over2 h.The effects of main reaction parameters (i.e. reactants stoi-chiometry, temperature, catalyst concentration) were assessed.The HOAc: glycerol molar ratio was varied over four different pro-portions (i.e.3:1; 6:1; 9:1 and 12:1 respectively). Control reactionswere performed for each molar proportion in the absence of cata-lyst. The activity of the most active HPA salt to the activity of metalnitrate and heteropolyacid precursor alone was also compared. |