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Chemical Structure| 106-61-6 Chemical Structure| 106-61-6

Structure of 106-61-6

Chemical Structure| 106-61-6

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Product Details of [ 106-61-6 ]

CAS No. :106-61-6
Formula : C5H10O4
M.W : 134.13
SMILES Code : OC(CO)COC(C)=O
English Name :2,3-Dihydroxypropyl acetate
MDL No. :MFCD00036185

Safety of [ 106-61-6 ]

Application In Synthesis of [ 106-61-6 ]

* 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.

  • Downstream synthetic route of [ 106-61-6 ]

[ 106-61-6 ] Synthesis Path-Downstream   1~14

  • 1
  • [ 64-19-7 ]
  • [ 56-81-5 ]
  • [ 106-61-6 ]
YieldReaction ConditionsOperation in experiment
89.2% With methanesulfonic acid In cyclohexane; butanone at 80℃; Large scale; 2 Esterification reaction Esterification raw material 9.2kgGlycerin and water-carrying agent 3kg butanone were added to a 30L atmospheric pressure reaction kettle, and the esterification reaction was carried out.It is a reversible reaction and produces water. In order to increase the conversion rate, water can be used to separate water from the reaction system. The material that can be used as a water-carrying agent must react with water to produce an azeotrope so that the water is more easily distilled out, and the solubility in water is small, and in this scheme, cyclohexane is used as a water-carrying agent.In addition, methanesulfonic acid was added to the reaction vessel as a catalyst for the esterification reaction, and the reaction vessel was heated to 80 ° C as a reaction temperature, and then 6 kg of another esterification raw material acetic acid was gradually added to the reaction vessel to cause it to occur. The esterification reaction produces glycerol monoacetate and water. Moreover, the reaction can be simultaneously applied to a reflux system with a water separator, and the water phase of the lower layer is separated by a water separator to obtain an oil phase of the upper layer, wherein the target product glycerin monoacetate is contained in the oil phase.The product in the reaction system can also be subjected to purification treatment. Specifically, the obtained oil phase is separated by a rectification column, and the water-carrying cyclohexane and the unreacted esterified raw material acetic acid in the oil phase are removed by vacuum distillation, and the heavy fraction at the bottom of the bottom is obtained. Pure glycerol monoacetate, the corresponding yield of this product is as high as 89.2%.
at 100℃; bei 114 stdg. Erhitzen;
With phosphoric acid at 170℃;
With phosphorus pentaoxide at 170℃;
With tetrachloromethane; phosphoric acid
die Bildung in der Kaelte im Laufe von mehreren Monaten nur spurenweise erfolgt;
With casein in der Kaelte;
29 %Chromat. With Amberlyst 15 In carbon dioxide at 110℃; Supercritical conditions;
With inorganic cat.
With magnesium oxide; potassium hydroxide

References: [1]Current Patent Assignee: SHENZHEN QIANHAI BOYANG RES INSTITUTE - CN108373410, 2018, A Location in patent: Paragraph 0025; 0033; 0034; 0035; 0036; 0043.
[2]Berthelot [Chimie organique, Bd.II <Paris 1860>,S.97] Berthelot [Annales de Chimie (Cachan, France), 1854, vol. <3> 41, p. 295][Annales de Chimie (Cachan, France), 1856, vol. 46, p. 482].
[3]Smith [Zeitschrift fur Physikalische Chemie, Stoechiometrie und Verwandtschaftslehre, 1922, vol. 102, p. 65].
[4]Schuette; Sah [Journal of the American Chemical Society, 1926, vol. 48, p. 3164].
[5]Schuette; Sah [Journal of the American Chemical Society, 1926, vol. 48, p. 3164].
[6]Schuette; Hale [Journal of the American Chemical Society, 1930, vol. 52, p. 1979].
[7]Berthelot [Chimie organique, Bd.II <Paris 1860>,S.97] Berthelot [Annales de Chimie (Cachan, France), 1854, vol. <3> 41, p. 295][Annales de Chimie (Cachan, France), 1856, vol. 46, p. 482].
[8]Guedras [Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1905, vol. 140, p. 1034].
[9]Location in patent: experimental part Rezayat, Marzieh; Ghaziaskar, Hassan S. [Green Chemistry, 2009, vol. 11, # 5, p. 710 - 715].
[10]Zada, Bakht; Joo, Seongjoon; Wang, Chonglong; Tseten, Tenzin; Jeong, Seong-Hee; Seo, Hogyun; Sohn, Jung-Hoon; Kim, Kyung-Jin; Kim, Seon-Won [Green Chemistry, 2020, vol. 22, # 22, p. 7788 - 7802].
[11]Manríquez-Ramírez, Ma Elena; Trejo-Valdez, Martin; Castro, Laura V.; Ortiz-Islas, Emma [Catalysis Letters, 2024, vol. 154, # 7, p. 3294 - 3308].
  • 2
  • [ 14739-11-8 ]
  • [ 106-61-6 ]
YieldReaction ConditionsOperation in experiment
88% With samarium(III) chloride In ethanol at 80℃; for 7h; sealed tube; Inert atmosphere; chemoselective reaction;
75% With sodium dodecyl-sulfate; benzyl bromide In water at 20℃; for 7h; chemoselective reaction;
52% With Trimethyl borate; boric acid at 90℃;
With hydrogenchloride In tetrahydrofuran for 3h; Ambient temperature;
1.35 g With acetic acid In water for 0.166667h; Heating; 4.9. (±)-1-Acetylglycerol (10) A mixture of (±)-9 (1.80 g, 10.3 mmol) and 80% acetic acid (10 mL) was stirred and heated at 130 °C (bath temperature) for 10 min. The resulting homogeneous solution was concentrated in vacuo. The residuewas mixed with toluene, and concentrated again in vacuo to remove toluene, acetic acid and water. The remaining oil (±)-10 (1.35 g, 97%) was used in the next step without further purification.

  • 3
  • [ 106-61-6 ]
  • [ 76855-69-1 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
86% With zinc diacetate In benzene for 8.5h; Heating;
  • 4
  • [ 106-61-6 ]
  • [ 76-83-5 ]
  • [ 121269-77-0 ]
YieldReaction ConditionsOperation in experiment
73% With dmap; triethylamine In dichloromethane
  • 5
  • [ CAS Unavailable ]
  • [ CAS Unavailable ]
  • [ 106-61-6 ]
  • [ 5704-66-5 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
With pyridine; hydrogenchloride In benzene Synthesis of DPAG Synthesis of DPAG DPAG was prepared by esterification of 1-acetyl-glycerol (1-monoacetin) with pyruvyl chloride. To a 250 ml three-neck flask fitted with a thermometer, a mechanical stirrer, a 25 ml dropping funnel, and flushed with dry nitrogen, one adds 5.0 g of anhydrous monoacetin (dried for 2 days under vacuum), 8.0 ml of anhydrous pyridine, and 100 ml of anhydrous benzene. The flask is cooled below 10° C. with an ice+salt slurry. Freshly distilled pyruvyl chloride (6.0 ml, 1 equivalent) is added dropwise over 15 min, while maintaining the temperature below 10° C. Then, the reaction mixture (showing a white precipitate of pyridinium chloride) is stirred for 1 hr at room temperature. The reaction mixture is filtered, to remove the pyridinium salt, and concentrated at 30° C. on a rotavapor under high vacuum. The crude yellow product is dissolved in 50 ml of chloroforn, washed once with 10 ml of HCl 1N, and stirred with 4 g of Amberlyst-15 for 4 hr. The solvent is evaporated on a rotavapor under high vacuum at 30 ° C. maximum. The yield of DPAG (light yellow oil) is 9.6 g (94%).
With pyridine; hydrogenchloride In chloroform; benzene Synthesis of DPAG Synthesis of DPAG DPAG was prepared by esterification of 1-acetyl-glycerol (1-monoacetin) with pyruvyl chloride. To a 250 ml three-neck flask fitted with a thermometer, a mechanical stirrer, a 25 ml dropping funnel, and flushed with dry nitrogen, one adds 5.0 g of anhydrous monoacetin (dried for 2 days under vacuum), 0.0 ml of anhydrous pyridine, and 100 ml of anhydrous benzene. The flask is cooled below 10° C. with an ice+salt slurry. Freshly distilled pyruvyl chloride (6.0 ml, 1 equivalent) is added dropwise over 15 min, while maintaining the temperature below 10° C. Then, the reaction mixture (showing a white precipitate of pyridinium chloride) is stirred for 1 hr at room temperature. The reaction mixture is filtered, to remove the pyridinium salt, and concentrated at 30° C. on a rotavapor under high vacuum. The crude yellow product is dissolved in 50 ml of chloroform, washed once with 10 ml of HCl 1N, and stirred with 4g of Amberlyst-15 for 4 hr. The solvent is evaporated on a rotavapor under high vacuum at 30° C. maximum. The yield of DPAG (light yellow oil) is 9.6 g (94%).
  • 6
  • [ 628-23-9 ]
  • [ 106-61-6 ]
YieldReaction ConditionsOperation in experiment
With acetic anhydride In pyridine 5 Preparation of 1-dibenzosuberanyl-4-(4-hydroxy-2-butynyl)piperazine (Compound 6) and 1-dibenzosuberanyl-4-(4-acetoxy-2-butynyl)piperazine (Compound 7) Example 5 Preparation of 1-dibenzosuberanyl-4-(4-hydroxy-2-butynyl)piperazine (Compound 6) and 1-dibenzosuberanyl-4-(4-acetoxy-2-butynyl)piperazine (Compound 7) 1,4-Butynediol (10 parts by weight) was dissolved in pyridine (200 parts by weight), and under ice cooling, acetic anhydride (20 parts by weight) was added dropwise. Subsequent to a reaction for 2 hours, the reaction mixture was concentrated under reduced pressure. The residue was purified by chromatography on a silica gel column (eluent: chloroform:ethyl acetate = 1:1) to yield monoacetin.
  • 7
  • [ 64-19-7 ]
  • [ 56-81-5 ]
  • [ 105-70-4 ]
  • [ 106-61-6 ]
  • [ 102-76-1 ]
YieldReaction ConditionsOperation in experiment
With Amberlyst 15 In carbon dioxide at 110℃; Supercritical conditions;
With tungstophosphoric acid/Cs2-ZrO2 at 120℃;
In acetic acid butyl ester at 110 - 130℃; for 5h; 2 Example 2; 472 g raw glycerin, by-product of the biodiesel process, with approximate composition shown in table III, containing 2.17 g free sulfuric acid as revealed by its strong acidity, was mixed with 909 g acetic acid, 90 g butyl acetate and 0.7 g 98% sulfuric acid, and heated up until total reflux. The vapors leaving the reaction mass were rectified in a column with 3 theoretical plates, condensed, and the organic and aqueous phases were continuously separated by decantation. The organic phase returned to the top of the column and the aqueous phase discarded. The operation lasted about 5 hours, the reaction mass temperature varying from 110 to 130 C, and 80 to 90C at the top of the column. The non-neutralized reaction mass, presenting a proportion among acetins as shown in table IV, was subject to flash distillation to remove the butyl acetate and the residual acetic acid. The butyl acetate was distilled at atmospheric pressure, with reaction mass temperature within 120-150C and 90-100C at the top of the column. The acetic acid was removed by reduced pressure distillation at 200-500 mm Hg, the reaction mass temperature within 90-120 C and 50-30 C at the top of the column. After recovery of the butyl acetate and the residual acetic acid, the proportion of the acetins reached new values as shown in table IV.
In acetic acid butyl ester at 110 - 130℃; 2 Example 2; 472 g raw glycerin, by-product of the biodiesel process, with approximate composition shown in table III, containing 2.17 g free sulfuric acid as revealed by its strong acidity, was mixed with 909 g acetic acid, 90 g butyl acetate and 0.7 g 98% sulfuric acid, and heated up until total reflux. The vapors leaving the reaction mass were rectified in a column with 3 theoretical plates, condensed, and the organic and aqueous phases were continuously separated by decantation. The organic phase returned to the top of the column and the aqueous phase discarded. The operation lasted about 5 hours, the reaction mass temperature varying from 110 to 130 0C, and 80 to 90 0C at the top of the column.The non-neutralized reaction mass, presenting a proportion among acetins as shown in table IV, was subject to flash distillation to remove the butyl acetate and the residual acetic acid. The butyl acetate was distilled at atmospheric pressure, with reaction mass temperature within 120-150 0C and 90-100 0C at the top of the column. The acetic acid was removed by reduced pressure distillation at 200-500 mm Hg, the reaction mass temperature within 90-120 0C and 50-30 0C at the top of the column. After recovery of the butyl acetate and the residual acetic acid, the proportion of the acetins reached new values as shown in table IV.Table III - Characteristics of the raw glycerin, biodiesel by-product.Table IV - Content of acetins in mixtureComments - example 2 shows that the process works with high volatile content glycerin, and that the high free mineral acidity in the form of sulfuric acid acts as catalyst. It also shows that the reaction continues during the recovery of both the azeotropic agent and the residual acetic acid.
at 100℃; for 1h; Ionic liquid;
With Ag(1+)*2H(1+)*PW12O40(3-)=AgH2PW12O40 at 120℃; for 0.25h; Autoclave; Green chemistry; 2.3 Catalytic tests General procedure: All the catalytic tests were conducted at atmospheric pressure. Esterification of glycerol with acetic acid was carried out in a 100ml stainless steel with Teflon liner autoclave under vigorous stirring. In a typical run, 0.05g catalyst, 5.0g glycerol, and 32.6g acetic acid were introduced into the reactor. Then, the reaction mixture was stirred and heated at 120°C for an appropriate reaction time. After reaction, the reactor system was rapidly cooled to room temperature in an ice-water bath. Subsequently, the solid catalyst was separated by centrifugation, and the liquid products were analyzed by a gas chromatography (Ruihong chromatogram analysis Co., Ltd, China) with a flame ionization detector using a DB-WAX capillary column. Concurrently, the assignment of the products was identified by a gas chromatography-mass spectrometry (Agilent, USA) with a DB-WAX capillary column.
With copolymer of polyhedral octavinylsilsesquioxane with sodium p-styrene sulfonate In toluene at 120℃; for 2h;
With sulfated alumina at 110℃; chemoselective reaction;
With 4,4′-trimethylenedipiperidinium hydrogen sulfate hydrate In cyclohexane at 80℃; 3.1 The Typical Esterification Procedure A mixture of glacial acetic acid (ReagentPlus, ≥ 99%,6.06 g, 5.78 mL, 100.0 mmol), glycerol solution(83.5-89.5% (T), 2.13 g, 1.7 mL, 20.0 mmol), and[TMDPH2]2+2[HSO4]-·H2O (0.21 g, 10 wt. %) were vigorouslystirred into cyclohexane (15.6 g, 20.0 mL) in a50 mL three-necked flask equipped with a reflux condenserat 80 °C under ambient pressure. After six hours, the liquidbi-phase formed in the flask. The cyclohexane phasewas quantitatively analyzed by a GC9790. The compositionsof the desired products were qualitatively identifiedby a GC-MS-QP2020. Each test has been carried outthree times. The reusability of the organic acid catalystwas investigated after the concentration of residue by arotary evaporator at 60 °C.
With sulfuric acid treated carbon prepared from end-of-life tires at 110℃; 3.4. Catalytic Tests The tire-derived carbons were tested as catalysts for glycerol esterification. The processwas performed under solventless conditions and atmospheric pressure in an Ar flow usingacetic acid (AA). AA (28.9 mL) was mixed with 0.7 g of a previously dried catalyst andheated to 110 C. After the desired temperature was reached, glycerol (Gly; 7.75 g; Gly:AAmolar ratio of 1:6) was added to the flask, and this time point was treated as t = 0 h. Tomonitor the process, aliquots of the reaction mixtures were withdrawn after different timeintervals (1, 2, 4, 6, and 24 h), and the catalyst was separated from the liquid mixture bycentrifugation. After dilution of the supernatant fluid with ethanol, the composition ofthe reaction mixture was analyzed employing an SRI 8610C gas chromatograph equippedwith a flame ionization detector (FID) and an InertCap WAX capillary column workingat a temperature range of 130-210 C under Ar flow. After finishing the esterificationprocess, the catalyst was recovered by filtration, washed with hot distilled water followedby washing with acetone, and dried overnight at 110 C. Afterward, it was used in asubsequent reaction cycle. To confirm the catalytic properties of the prepared samples, ablank test (without a catalyst) was also performed. For the sake of comparison, modifiedcommercial carbon black (CB-SA) was also tested. The catalytic performances of thesamples were expressed as the conversion of glycerol (XGly), selectivities to various acetins(SMA, SDA, and STA), and/or yields of different products (YMA, YDA, and YTA).
With ZnNb2O6 at 80℃;

References: [1]Location in patent: experimental part Rezayat, Marzieh; Ghaziaskar, Hassan S. [Green Chemistry, 2009, vol. 11, # 5, p. 710 - 715].
[2]Location in patent: experimental part Jagadeeswaraiah; Balaraju; Prasad, P.S. Sai; Lingaiah [Applied Catalysis A: General, 2010, vol. 386, # 1-2, p. 166 - 170].
[3]Current Patent Assignee: RHODIA POLIAMIDA E ESPECIALIDADES LTDA - EP2272818, 2011, A1 Location in patent: Page/Page column 7.
[4]Current Patent Assignee: RHODIA POLIAMIDA E ESPECIALIDADES LTDA - WO2011/1249, 2011, A1 Location in patent: Page/Page column 12-13.
[5]Location in patent: experimental part Liu, Xiumei; Ma, Huiyuan; Wu, Yue; Wang, Chang; Yang, Miao; Yan, Peifang; Welz-Biermann, Urs [Green Chemistry, 2011, vol. 13, # 3, p. 697 - 701].
[6]Zhu, Shanhui; Gao, Xiaoqing; Dong, Fang; Zhu, Yulei; Zheng, Hongyan; Li, Yongwang [Journal of Catalysis, 2013, vol. 306, p. 155 - 163].
[7]Leng, Yan; Zhao, Jiwei; Jiang, Pingping; Lu, Dan [Catalysis science and technology, 2016, vol. 6, # 3, p. 875 - 881].
[8]Pankajakshan, Arun; Pudi, Satyanarayana Murty; Biswas, Prakash [International Journal of Chemical Kinetics, 2018, vol. 50, # 2, p. 98 - 111].
[9]Zaharani, Lia; Mihankhah, Peyman; Johan, Mohd Rafie; Khaligh, Nader Ghaffari [Catalysis Letters, 2024, vol. 154, # 5, p. 2314 - 2327].
[10]Malaika, Anna; Kowalska-Kuś, Jolanta; Końska, Klaudia; Ptaszyńska, Karolina; Jankowska, Aldona; Held, Agnieszka; Wróblewski, Krzysztof; Kozłowski, Mieczysław [Molecules, 2023, vol. 28, # 24].
[11]Bertoldo, Gabriela Mota; Oliveira, Alcineia Conceição; Saraiva, Gilberto Dantas; Jucá, Rai; da Silva Filho, José Gadelha; Rodríguez-Aguado, Elena; Jiménez-Jiménez, José; Rodríguez-Castellón, Enrique [Dalton Transactions, 2024, vol. 53, # 21, p. 9139 - 9150].
  • 8
  • [ 64-19-7 ]
  • [ 56-81-5 ]
  • [ 105-70-4 ]
  • [ 106-61-6 ]
YieldReaction ConditionsOperation in experiment
With tungstophosphoric acid/Cs2-ZrO2 at 60℃;
With ZSM-5 at 120℃; for 0.25h;
With bichar acid catalyst synthesized by carbonization of Palmyra palm fruit shells at 400 °C at 100℃; for 4h; 2.3.Procedure of reaction performance The investigation of glycerol esterification under atmospheric pressure was conducted within a liquid phase setting. In a standard test, a round-bottom flask was filled with 0.20 gm of catalyst, 9.78 gm of acetic acid and 5 gm of glycerol. We used gas chromatography with flame ionization detectors (FIDs) to monitor the reaction progression and sort the products, while Equity-5 columns were used for exact analysis.
  • 9
  • [ 64-19-7 ]
  • [ 56-81-5 ]
  • [ 106-61-6 ]
  • [ 100-78-7 ]
YieldReaction ConditionsOperation in experiment
1: 71.9% 2: 8.8% With Dowex 50Wx2 at 104.84℃; 2.2.1 Standard esterification tests The esterification reactions were carried out at 378 K and atmospheric pressure in a round bottom flask reactor equipped with a magnetic stirrer and placed in an oil bath. The acetic acid (puriss. p.a., ACS reagent, ≥99.8%, GC/T, Fluka) concentration was 100 g/l of glycerol (puriss. p.a., ACS reagent, anhydrous, dist., ≥99.5%, Fluka) which corresponds to an initial molar ratio acetic acid:glycerol = 1:8; the dried catalyst concentration being 0.25 g/40 ml of glycerol. Samples of the reaction medium were analysed by gas chromatography Cp-Sil 8CB with a FID detector, after extraction with 1-heptanol (98%, Sigma-Aldrich) using o-xylene (98%, Aldrich) as the internal standard. The activity results are presented in terms of conversion of acetic acid. Carbon balance results in an error near 20%, likely due to losses of acetic acid by evaporation during the injection or during the reaction. This is highly probable as acetic acid is the most volatile molecule in the system. (0012) The test procedure was as follows: the catalyst dried overnight at 378 K under vacuum was put in the reactor together with the glycerol and the mixture was brought to the reaction temperature. When the temperature was reached, acetic acid was injected. One minute after the injection, a sample was taken and analysed. This result was considered as the initial chemical composition of the medium. This process was necessary to exclude the possibility that the catalytic measurements were interfered with the disappearance of acetic acid due to evaporation phenomena during its injection.
at 100℃; for 0.5h;
With sulphated zirconia with hydrolysis ratio = 6 at 54.84℃; for 24h;
In toluene at 105℃; for 1h;

  • 10
  • [ 64-19-7 ]
  • [ 56-81-5 ]
  • [ 105-70-4 ]
  • [ 106-61-6 ]
  • [ 100-78-7 ]
  • [ 102-62-5 ]
  • [ 102-76-1 ]
YieldReaction ConditionsOperation 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 %.

References: [1]Location in patent: experimental part Ferreira; Fonseca; Ramos; Vital; Castanheiro [Catalysis Communications, 2011, vol. 12, # 7, p. 573 - 576].
[2]Location in patent: experimental part Trejda, MacIej; Stawicka, Katarzyna; Dubinska, Anna; Ziolek, Maria [Catalysis Today, 2012, vol. 187, # 1, p. 129 - 134].
[3]Trejda, Maciej; Stawicka, Katarzyna; Ziolek, Maria [Catalysis Today, 2012, vol. 192, # 1, p. 130 - 135].
[4]Gao, Xiaoqing; Zhu, Shanhui; Li, Yongwang [Catalysis Communications, 2015, vol. 62, p. 48 - 51].
[5]Kale; Umbarkar; Dongare; Eckelt; Armbruster; Martin [Applied Catalysis A: General, 2015, vol. 490, # 1, p. 10 - 16].
[6]De La Calle, Carlos; Fraile, José M.; García-Bordejé, Enrique; Pires, Elísabet; Roldán, Laura [Catalysis science and technology, 2015, vol. 5, # 5, p. 2897 - 2903].
[7]Huang, Ming-Yu; Han, Xiao-Xiang; Hung, Chin-Te; Lin, Jann-Chen; Wu, Pei-Hao; Wu, Jung-Chung; Liu, Shang-Bin [Journal of Catalysis, 2014, vol. 320, p. 42 - 51].
[8]Huang, Ming-Yu; Han, Xiao-Xiang; Hung, Chin-Te; Lin, Jann-Chen; Wu, Pei-Hao; Wu, Jung-Chung; Liu, Shang-Bin [Journal of Catalysis, 2014, vol. 320, # 1, p. 42 - 51].
[9]Kale; Armbruster; Eckelt; Bentrup; Umbarkar; Dongare; Martin [Applied Catalysis A: General, 2016, vol. 527, p. 9 - 18].
[10]Morais, Eduardo M.; Grillo, Igor B.; Stassen, Hubert K.; Seferin, Marcus; Scholten, Jackson D. [New Journal of Chemistry, 2018, vol. 42, # 13, p. 10774 - 10783].
[11]Neto, Antonio B.S.; Oliveira, Alcineia C.; Rodriguez-Castellón, Enrique; Campos, Adriana F.; Freire, Paulo T.C.; Sousa, Francisco F.F.; Filho, Josué M.; Araujo, Jesuina C.S.; Lang, Rossano [Catalysis Today, 2020, vol. 349, p. 57 - 67].
[12]Rigo, Davide; Calmanti, Roberto; Perosa, Alvise; Selva, Maurizio [Green Chemistry, 2020, vol. 22, # 16, p. 5487 - 5496].
[13]Soares Dias, Ana Paula; Gomes Fonseca, Frederico; Catarino, Mónica; Gomes, João [Catalysis Letters, 2022, vol. 152, # 2, p. 513 - 522].
[14]Yadav, Ganapati D.; Katole, Suraj O. [Journal of the Indian Chemical Society, 2025, vol. 102, # 4].
  • 11
  • [ 106-61-6 ]
  • [ 18162-48-6 ]
  • [ 1448674-97-2 ]
YieldReaction ConditionsOperation in experiment
46% With dmap; triethylamine In dichloromethane at 20℃; 3.84.1 Step 1: 3-[tert-Butyl(dimethyl)silyl]oxy}-2-hydroxypropyl acetate (3_84_2) Step 1: 3-[tert-Butyl(dimethyl)silyl]oxy}-2-hydroxypropyl acetate (3_84_2) [00527] Tert-butyldimethylchlorosilane (TBSC1, 28.2 g, 180.1 mmol) was added portion wise to a mixture of compound 3_84_1 (27 g, 189.6 mmol; ref.: /. Med. Chem. 1989, 2104-2110), triethylamine (36.9 mL, 265.4 mmol) and 4- dimethylaminopyridine (1.38 g, 11.4 mmol) in dichloromethane (250 mL). The reaction mixture was stirred at room temperature overnight, filtered and the filtrate was concentrated. The residue was dissolved in EtOAc, filtered again to remove any solid, and the filtrate was concentrated to give a residue, which was purified by column chromatography eluting with 30% EtOAc in hexane to give compound 3_84_2 (22 g, 46 % yield) as an oil. [00528] NMR (400 MHz, CDC13): δ = 0.07 (s, 6 H), 0.89 (s, 9 H), 2.08 (s, 3 H), 2.49 (d, J=5.5 Hz, 1 H), 3.57 - 3.65 (m, 1 H), 3.65 - 3.73 (m, 1 H), 3.82 - 3.93 (m, 1 H), 4.04 - 4.21 (m, 2 H).
  • 12
  • [ 64-19-7 ]
  • [ 56-81-5 ]
  • [ 106-61-6 ]
  • [ 102-62-5 ]
YieldReaction ConditionsOperation 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;
  • 13
  • [ 64-19-7 ]
  • [ 56-81-5 ]
  • [ 106-61-6 ]
  • [ 102-62-5 ]
  • [ 102-76-1 ]
YieldReaction ConditionsOperation 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;
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  • [ 79-20-9 ]
  • [ 56-81-5 ]
  • [ 105-70-4 ]
  • [ 106-61-6 ]
  • [ 100-78-7 ]
  • [ 102-62-5 ]
  • [ 102-76-1 ]
YieldReaction ConditionsOperation 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.
 

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