1,3-Dioxolane-4-methanol

Will be 920g of glycerin, 990gParaformaldehyde and20 g of the supported solid super acid catalyst prepared in was addedIn the reaction device, the reaction is heated to 80 ° C, and the water having a lower boiling point and the trioxane formed in the reaction process enters the fractionation device.According to the principle that the boiling point of paraformaldehyde is lower than water, the triacetal is fractionated back to the reaction unit through a fractionation device.The reaction was carried out as a raw material, and the reaction was completed for 5 hours to obtain glycerol formal, and the product was analyzed by HPLC-MS.At 96.3percent, the ratio of the six-membered ring product to the product of the five-membered ring in the product was 70:25.A 250 mL three neck flask equipped with a stirrer, an addition funnel, and a Dean-Stark trap was charged with glycerol (9.2 g, 0.1 mol), paraformaldehyde (2.7 g, 0.09 mol), activated ion exchange resin Dowex 50 (10 wt.%), and anhydrous toluene (70 mL). The reaction mixture was refluxed until calculated amount of water was distilled off. The mixture was cooled and filtered. The solvent was removed in low vacuum. Distillation of the residue afforded a mixture of compounds 1a and 1b in the yield of 9.2 g (93%), b.p. 190-195 C (760 Torr). An isomeric ratio was determined by 1H NMR spectroscopy from the integrated intensity ratio of the signals of H(4) methyne protons (deltaH 3.5-4.0) of dioxolane 1a and H(5) methyne proton (deltaH 3.5-4.0) of dioxane 1b. Compound 1a. MS (EI, 70 eV), m/z (Irel (%)): 103 [M - H]+ (not detected), 73 (75), 57 (15), 45 (100), 31 (15). Compound 1b. MS (EI, 70 eV), m/z (Irel (%)): 103 [M - H]+ (not detected), 87 (1), 74 (31), 45 (17), 44 (100), 31 (12).920 g of glycerin, 990 g of trioxane and 20 g of the supported solid superacid catalyst prepared in were charged into a reaction apparatus, and heated to 80 ° C to react, and the lower boiling water and trioxane formed during the reaction were fractionated. The device, according to the principle that the boiling point of the paraformaldehyde is lower than water, the triacetal is fractionated back to the reaction device through the fractionation device to continue the reaction as a raw material, and the reaction is finished for 5 hours, thereby obtaining glycerol formal, which is analyzed by HPLC-MS. The yield of the product was 93.5percent, and the ratio of the product of the six-membered ring product to the product of the five-membered ring was 77:23.General procedure: In a 50-mL flask equipped with a 20-mL dropping funnel, 3.19 g of a mixture of 1, 3-dioxan-5-ol and 4-hydroxymethyl-1, 3-dioxolane (a trade name: Glycerol Formal, manufactured by Tokyo Chemical Industry Co., Ltd., purity: 98.0%, 30.0 mmol; Reference Literature 1 (Journal of Catalysis, Vol. 245, pp.428-435, 2007) describes 1H-NMR signal assignment of a proton at the 2-position of two kinds of isomers, and an isomer ratio of 1, 3-dioxan-5-ol to 4-hydroxymethyl-1, 3-dioxolane determined from this information and the 1H-NMR analysis was 58/42), 4.7 mg of 2-hydroxy-2-azaadamantane (AZADOL, a trademark, manufactured by Nissan Chemical Corporation, purity: 98.0%, 30 mumol), 4.92 g of 3, 5-lutidine (purity: 98.0%, 45.0 mmol), and 10 g of 2-butanone were charged and stirred in a nitrogen atmosphere while cooling. A solution of 2.94 g of TCCA (purity: 95.0%, 12.0 mmol) dissolved in 10 g of 2-butanone was charged in the dropping funnel and dropped over 1 hour while regulating a dropping rate such that the reaction solution temperature within the flask fell within a range of from -10 C. to 10 C. The cooling was stopped, and the stirring was further continued for 2 hours while raising the reaction solution temperature to around 25 C. Finally, 0.20 g of 2-propanol (purity: 99.7%, 3.3 mmol) was added, and the stirring was further performed for 10 minutes, thereby completing the reaction. After filtering off a by-produced powdered solid, the filtrate was subjected to GC analysis. As a result, the conversion of 4-hydroxymethyl-1, 3-dioxolane was 100%, the yield of (1, 3-dioxolan-4-yl)methyl 1, 3-dioxolane-4-carboxylate was 91%, and the recovery of the unreacted 3, 5-lutidine relative to the charged amount was 18%. (0162) In a stirred mixed liquid of 50 g of tert-butyl methyl ether having the whole amount of the filtration residue dispersed therein and 25 g of ion exchanged water, a 2 mol/L sodium hydroxide aqueous solution was dropped until the pH of the water layer became 12 or more. At the time of completion of dropping, the filtration residue was dissolved in oily water. As a result of GC analysis of the tert-butyl methyl ether solution from which the water layer had been removed through oil-water separation, the recovery of the 3, 5-lutidine relative to the charged amount was 76%, and a total recovery was 94%.The above glycerol formal is added to a 5 L reaction kettle, and an A15 resin acid catalyst (10% by mass of glycerol formal) is added to the kettle, and isobutylene (3 equivalents, equivalent to glycerol formal) is introduced. And pass a certain amount of nitrogen.The stirring was started, the temperature was raised to 70 C, and the reaction was carried out at this temperature for 8 hours. The reaction was stopped and the mixture was cooled to room temperature to recover isobutylene. The catalyst was removed by filtration and the pH was adjusted to 7. Distillation under reduced pressure gave the product A in a yield of 84%.

Molecular Weight:104.10
XLogP3:-0.8
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:1
Exact Mass:104.047344113
Monoisotopic Mass:104.047344113
Topological Polar Surface Area:38.7
Heavy Atom Count:7
Complexity:54.9
Undefined Atom Stereocenter Count:1
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes