* 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.
Reference:
[1] Journal of the American Chemical Society, 2015, vol. 137, # 11, p. 3767 - 3770
[2] Journal of the American Chemical Society, 2015, vol. 137, # 11, p. 3767 - 3770
[3] Journal of the American Chemical Society, 2015, vol. 137, # 11, p. 3767 - 3770
[4] Journal of the American Chemical Society, 2018, vol. 140, # 2, p. 748 - 757
2
[ 111-46-6 ]
[ 3041-16-5 ]
Reference:
[1] Synlett, 2012, vol. 23, # 15, p. 2261 - 2265
[2] Journal of the American Chemical Society, 2015, vol. 137, # 11, p. 3767 - 3770
[3] Angewandte Chemie - International Edition, 2011, vol. 50, # 15, p. 3533 - 3537
[4] Journal of Organic Chemistry, 2004, vol. 69, # 15, p. 5116 - 5119
[5] Catalysis Communications, 2012, vol. 20, p. 68 - 70
[6] Green Chemistry, 2009, vol. 11, # 6, p. 793 - 797
[7] Journal of the American Chemical Society, 2013, vol. 135, # 20, p. 7593 - 7602
[8] Journal of the American Chemical Society, 2018, vol. 140, # 2, p. 748 - 757
[9] Journal of Organic Chemistry, 1999, vol. 64, # 18, p. 6750 - 6755
[10] Bulletin of the Chemical Society of Japan, 2001, vol. 74, # 1, p. 165 - 172
[11] Patent: WO2009/17261, 2009, A1, . Location in patent: Page/Page column 5
[12] Patent: US2010/4471, 2010, A1, . Location in patent: Page/Page column 3
[13] Patent: KR2016/53097, 2016, A, . Location in patent: Paragraph 0026-0027
[14] Patent: US2807629, 1953, ,
3
[ 16024-56-9 ]
[ 3041-16-5 ]
Reference:
[1] Chemical Research in Toxicology, 2012, vol. 25, # 5, p. 1022 - 1028
[2] Chemische Berichte, 1932, vol. 65, p. 923
4
[ 123-91-1 ]
[ 3041-16-5 ]
Reference:
[1] Journal of Organic Chemistry, 1999, vol. 64, # 12, p. 4509 - 4511
[2] Tetrahedron Letters, 1995, vol. 36, # 49, p. 9071 - 9072
[3] Journal of Chemical Research, Miniprint, 1983, # 7, p. 1701 - 1720
5
[ 95-59-0 ]
[ 3041-16-5 ]
Reference:
[1] Journal of the American Chemical Society, 1958, vol. 80, p. 604
6
[ 123-91-1 ]
[ 22347-47-3 ]
[ 3041-16-5 ]
Yield
Reaction Conditions
Operation in experiment
90 %Chromat.
at 80℃; for 24 h;
In a typical experiment, oxidation of 1,4 dioxane with O2 was performed in a 25 mL two-necked round bottom flask equipped with a reflux condenser; filled with 10 mmol of 1,4 dioxane, and 150 mg of catalyst. The reaction mixture was heated at 80 °C under gentle stirring. At atmospheric pressure, O2 gas from a balloon was bubbled into the reaction mixture at a certain stable flow rate controlled by a mass flow controller. Care should be taken while heating the reaction mixture as dioxane vapours can form a highly combustible mixture with pure oxygen and form explosive peroxides (MSDS 1,4 dioxane). After 24 h, the catalyst was separated from the reaction mixture by simple filtration and the reaction mixture after proper dilution with methanol was analyzed using GC–MS.
Reference:
[1] Russian Chemical Bulletin, 2005, vol. 54, # 10, p. 2384 - 2393
[2] Catalysis Communications, 2017, vol. 90, p. 56 - 59
7
[ 13382-47-3 ]
[ 3041-16-5 ]
Reference:
[1] Journal of Materials Chemistry, 2007, vol. 17, # 38, p. 4050 - 4056
8
[ 14869-41-1 ]
[ 3041-16-5 ]
Reference:
[1] Suomen Kemistilehti B, 1944, vol. 17, p. 18[2] Chem.Abstr., 1946, p. 6491
9
[ 56127-61-8 ]
[ 3041-16-5 ]
[ 75-36-5 ]
Reference:
[1] Journal of the American Chemical Society, 1958, vol. 80, p. 604
10
[ 111-46-6 ]
[ 497-26-7 ]
[ 123-91-1 ]
[ 543-75-9 ]
[ 3041-16-5 ]
Reference:
[1] Chemistry of Heterocyclic Compounds, 1996, vol. 32, # 1, p. 23 - 29
[2] Chemistry of Heterocyclic Compounds, 1996, vol. 32, # 1, p. 23 - 29
11
[ 3041-16-5 ]
[ 142047-97-0 ]
Reference:
[1] Chemical Research in Toxicology, 2012, vol. 25, # 5, p. 1022 - 1028
With hydrogen; at 230 - 255℃; for 30 - 980h;Product distribution / selectivity;
Example 1-1[22] A catalyst tower made of a cylindrical stainless tube measuring 9 cm in internal diameter and 160 cm in height, in which 8 kg of a catalyst had been loaded, was equipped at a 2OL reactor. Then, 15 kg of diethylene glycol was supplied to the reactor. Hydrogen was supplied to the catalyst tower through the reactor at a rate of 600 mL per minute. The reactor and the catalyst tower were heated to a temperature of 230-2350C and 245-2550C, respectively.[23] By controlling the heat source of the reactor, diethylene glycol was vaporized so that the diethylene glycol could be supplied at a rate of 450-470 mL per hour. After 30 hours of reaction, 1431 g of a crude p-dioxanone product was obtained from the catalyst tower. Conversion ratio was 96 % and selectivity was 94 %. Example 1-2[25] After 980 hours of catalytic reaction in the same manner as in Example 1-1, 1416 g of a crude p-dioxanone product was obtained. Conversion ratio was 97 % and selectivity was 91 %.
With copper chromite;Reflux;
EXAMPLE; About 36.8 grams of crude p-dioxanone was produced following the procedures set forth in U.S. Pat. No. 5,391,768, having a purity of about 57.6 mol % (thus having about 0.144 moles, or 42.4%, of diethylene glycol). Briefly, about 130 grams of diethylene glycol (DEG) and about 2 grams of copper chromite were refluxed for about 6 hours. The reaction mixture was distilled and a crude p-dioxanone with a purity of about 57.6 mol % (42.4 mol % DEG) was collected. About 3.7 grams (about 10% by weight) of 1,4-phenylene diisocyanate from Sigma Aldrich was combined with about 36.8 grams of crude p-dioxanone in a 100 mL flask and stirred for about 3 hours at about 22 C. under a nitrogen blanket. The reaction was monitored in situ by Fourier Transform Infrared Spectroscopy (FT-IR) using a REACTIR 4000 Spectrometer (Mettler-Toledo AutoChem, Columbia, Md.), as well as proton nuclear magnetic resonance spectroscopy (1H-NMR) run at about 300 MHz; the ReactIR probe was inserted into the flask; the background utilized was air.The IR results showed a peak indicative of free NCO groups, at 2266 cm-1, which decreased during the course of the reaction. After about 1.5 hours, there was no peak from NCO groups due to their reaction with the hydroxyl compounds. The 1H-NMR spectra of the starting crude p-dioxanone showed about 57.6 mol % purity; after about 3 hours of reacting with 1,4-phenylene diisocyanate, the purity was increased to about 61.9 mol %. The reaction mixture was left for about 72 hours without stirring. The 1H-NMR spectra obtained after about 72 hours showed no change in the molar percentage of the p-dioxanone in the reaction mixture.
With hydrogen; at 280℃;
On top of a catalyst bed comprising a cylindrical stainless steel tube having an inner diameter of 6 cm and a height of 100 cm equipped with 5 kg of a copper-chromium (Cu-Cr) catalyst, DEG was introduced at a rate of 2.0 ml / min using a metering pump, and hydrogen was introduced at a flow rate of 2.5 L / min using a flow meter. The catalyst bed was heated via a block heater to a temperature of 280 C. The crude para-dioxanone discharged to the bottom was recovered, sampled daily, and the purity was measured by gas chromatography. The purity measurement results are shown in Fig. According to FIG. 2, the purity of crude para-dioxanone was 75% at the beginning of the reaction, but then decreased to 50% after 25 days. From this, it can be seen that the lifetime of the catalyst was drastically reduced as the reaction time elapsed.
EXAMPLE 2 A feed mixture of diethylene gylcol and N-benzyl-2-(2-hydroxyethoxy)acetamide containing a small amount of p-dioxanone was prepared by adding 43.9 g. (0.41 g. mole) of benzylamine to a solution of 46 g. (0.45 g. mole) of p-dioxanone in 54 g. of diethylene glycol and heating the mixture on a water bath to complete the reaction after the initial exotherm was past.
In hexane; isopropyl alcohol; at 4 - 15℃;Purification / work up;
Example 2[27] Recrystallization of crude reaction product including p-dioxanone[28] Example 2-1[29] 6.5 kg of hexane and 16 kg of isopropyl alcohol were added into a 50 L reactor. The mixture solvent was cooled to 40C. Then, 17 kg of the crude p-dioxanone product with a purity of 92 wt% was added while maintaining the temperature of the reactor at 150C or below. After 1.5 hours of aging at 50C, the resultant p-dioxanone crystal was filtered at about 150C. Then, 14.7 kg of recrystallized p-dioxanone was obtained by washing 3 times with 4 kg of the mixture solvent of 1O0C. Gas chromatography analysis showed that the purity of p-dioxanone excluding the solvent was 99.992 wt% (area ratio). Example 2-2[31] 14.2 kg of recrystallized p-dioxanone was obtained in the same manner as inExample 2-1, except for using crude p-dioxanone with a purity of 90 wt% instead of the crude p-dioxanone of 92 wt%. Gas chromatography analysis showed that the purity of p-dioxanone excluding the solvent was 99.993 wt% (area ratio). Example 2-3[33] 15.8 kg of recrystallized p-dioxanone was obtained in the same manner as inExample 2-1, except for using a mixture solvent of 9.2 kg of hexane and 13.8 kg of isopropyl alcohol. Gas chromatography analysis showed that the purity of p-dioxanone excluding the solvent was 99.991 wt% (area ratio).
With sodium tetrahydroborate; In hexane; isopropyl alcohol; at 50℃; under 1 - 2 Torr;Purification / work up;
Example 3-2[41] 12.1 kg of p-dioxanone was obtained in the same manner as in Example 3-1, except for using 14 kg of recrystallized p-dioxanone with a purity of 99.984 wt% (area ratio) and adding 1.32 g of NaBH . Gas chromatography analysis showed that the purity of4 p-dioxanone excluding the solvent was 99.990 wt% (area ratio).
With aluminium hydride; In hexane; isopropyl alcohol; at 50℃; under 1 - 2 Torr;Purification / work up;
Example 3-3[43] 12.8 kg of recrystallized p-dioxanone was obtained in the same manner as inExample 3- 1 , except for using 14.4 kg of recrystallized p-dioxanone with a purity of 99.984 wt% (area ratio) and adding 0.98 g of AlH . Gas chromatography analysis showed that the purity of p-dioxanone excluding the solvent was 99.994 wt% (area ratio).
In isopropyl alcohol; at 4 - 15℃;Purification / work up;
Comparative Example[35] 13.4 kg of recrystallized p-dioxanone was obtained in the same manner as inExample 2-1, except for using 22 kg of isopropyl alcohol as solvent. Gas chromatography analysis showed that the purity of p-dioxanone excluding the solvent was 99.987 wt% (area ratio).
In a typical experiment, oxidation of 1,4 dioxane with O2 was performed in a 25 mL two-necked round bottom flask equipped with a reflux condenser; filled with 10 mmol of 1,4 dioxane, and 150 mg of catalyst. The reaction mixture was heated at 80 C under gentle stirring. At atmospheric pressure, O2 gas from a balloon was bubbled into the reaction mixture at a certain stable flow rate controlled by a mass flow controller. Care should be taken while heating the reaction mixture as dioxane vapours can form a highly combustible mixture with pure oxygen and form explosive peroxides (MSDS 1,4 dioxane). After 24 h, the catalyst was separated from the reaction mixture by simple filtration and the reaction mixture after proper dilution with methanol was analyzed using GC-MS.
EXAMPLE III A reaction vessel fitted with a condenser, and an agitator is charged with a solution of 4 parts of dinitrogen tetraoxide in 250 parts of chloroform. Into the agitated solution, about 10 parts of <strong>[3041-16-5]p-dioxanone</strong> is slowly added while the temperature is kept below 30C. In the next 24 hours, an additional 4 parts of dinitrogen tetraoxide is added, and the reaction is allowed to proceed for another 50 hours at 20-30C. The reaction mixture is then stripped off all nitrogen oxides by bubbling air through the system. Diglycolic acid is recovered by filtration at a yield of about 75%.
In 1,4-dioxane; at 5 - 20℃; for 2.08333h;Product distribution / selectivity;
Example 1; 2-hydroxyethoxy-acetic acid -N,N-dimethylamide; Into a round-bottom flask of the volume of 100 ml are transferred 50 ml dioxane and the solvent is cooled to 5 0C. Subsequently 8,1 g (0,18 mole) dimethylamine is absorbed in the solvent at the temperature of 5-10 0C in 20 minutes. To the solution of dimethylamine, 10.2 g (0.1 mole) of [l,4]-dioxane-2-one are added at the same temperature in 5 minutes and the reaction mixture is stirred at room temperature for 2 hours. After the reaction period, the solvent is evaporated in vacuo at the temperature of 50 0C in one hour. Thus 14.1 g (95.9%) of the title product are obtained, which has the purity of 98% as determined by gas chromatography. Optionally the product can be purified by distilling in vacuo (boiling temperature 130-135 0C/ 13 Pa). The raw product is directly suitable for the preparation of 2-chloroethoxy-acetic acid-nu,nu-dimethyl-amide.1H-NMR (CDCl3): delta= 2,94 (s), 2,99 (s), 3,6 (m), 3,7 (m), 4,26 (s) ppm. <n="14"/>Elemental Analysis:Calculated: C: 48.96%; H: 8.90%; N: 9.52%.Measured: C: 49.20%; H: 8.90%; N: 9.32%.
61.4%
In acetonitrile; at 5 - 20℃; for 2.08333h;Product distribution / selectivity;
Example 5; 2-hydroxyethoxy-acetic acid N,N-dimethylamide; The procedure of Example 1 is followed with the difference that instead of dioxane, acetonitrile is used as solvent. Yield 9.0 g (61.4 %). The quality of the product is identical with that obtained by the process of Example 1.
59.8%
In tetrahydrofuran; at 5 - 20℃; for 2.08333h;Product distribution / selectivity;
Example 3; 2-hydroxyethoxy-acetic acid-N,N-dimethylamide; The procedure of Example 1 is carried out with the difference that instead of dioxane, tetrahydrofurane is used as solvent. Yield, 8.8 g (59.8 %). The quality of the product is identical in with that of the product obtained by the process of Example 1.
50.4%
In ethanol; at 5 - 20℃; for 2.08333h;Product distribution / selectivity;
Example 2; 2-hydroxyethoxy-acetic acid-N,N-dimethylamide; The process of Example 1 is carried out with the difference that instead of dioxane, ethanol is used as solvent. Thus 7.4 g (50.4%) of the product are obtained. The quality of the product is identical to that obtained by the process of Example 1.
40.6%
In toluene; at 5 - 20℃; for 2.08333h;Product distribution / selectivity;
Example 4; 2-hydroxyethoxy-acetic acid N,N-dimethylamide; The procedure of Example 1 is followed with the difference that instead of dioxane, toluene is used as solvent and that the evaporation of the solvent is carried out at 80 0C instead of 50 0C in 4 hours. In this case, the yield is 6.0 g (40.6 %). The quality of the product is identical with those obtained by the process of Example 1.
α,ω-dihydroxy oligo(p-dioxanone), prepared by ring-opening polymerization with ethylene glycol as initiator and dibutyltin oxide as catalyst, Mn = 2100 g/mol (GPC); monomer(s): p-dioxanone; ethylene glycol[ No CAS ]
α,ω-dihydroxy oligo(p-dioxanone), prepared by ring-opening polymerization with ethylene glycol as initiator and dibutyltin oxide as catalyst, Mn = 2200 g/mol (GPC); monomer(s): p-dioxanone; ethylene glycol[ No CAS ]
With hydrogen bromide; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate;
Example 29 Synthesis of (2-Bromo-ethoxy)-acetic acid To 48% hydrobromic acid (372 ml) at 0 C. was added drop wise concentrated sulphuric acid (84.1 ml) and stirred for 10 minutes. At this temperature was added para dioxanone (70 grams, 685.6 mmol) followed by further stirring at room temperature for 1 hour. The reaction mixture was then was heated at 100 C. for 2 hours 30 minutes, followed by overnight cooling at room temperature. The reaction mixture was taken in to ice water, extracted with ethyl acetate (4*250 ml), dried over sodium sulphate, distilled to get crude acid 29 (98 grams) with a GC purity of 78.1%, which was fractionated under high vacuum two times to get 50 grams of acid 29 as a light yellow liquid with a purity of 90% as determined by gas chromatography (GC). The pure product 29 was also characterized using 1H NMR spectroscopy in CDCl3: delta 3.49(t, 2H, CH2), 3.89 (t, 2H, CH2), 4.20 (s, 2H, CH2), 8.56 (bs, 1H,COOH).
With sulfuric acid; hydrogen bromide; at 0 - 100℃; for 3.5h;
To 48% hydrobromic acid (372 ml) at 0 C. was added drop wise concentrated sulphuric acid (84.1 ml) and stirred for 10 minutes. At this temperature was added para dioxanone (70 grams, 685.6 mmol) followed by further stifling at room temperature for 1 hour. The reaction mixture was then was heated at 100 C. for 2 hours 30 minutes, followed by overnight cooling at room temperature. The reaction mixture was taken in to ice water, extracted with ethyl acetate (4×250 ml), dried over sodium sulphate, distilled to get crude acid 29 (98 grams) with a GC purity of 78.1%, which was fractionated under high vacuum two times to get 50 grams of acid 29 as a light yellow liquid with a purity of 90% as determined by gas chromatography (GC). The pure product 29 was also characterized using 1H NMR spectroscopy in CDCl3: delta 3.49 (t, 2H, CH2), 3.89 (t, 2H, CH2), 4.20 (s, 2H, CH2), 8.56 (bs, 1H, COOH).
With Novozym 435, lipase Candida antarctica B (CALB) immobilized on methacrylate macroporous resin; at 60℃; for 12h;Inert atmosphere;Thermodynamic data; Kinetics; Catalytic behavior;
General procedure: Typically, the ROP of <strong>[3041-16-5]PDO</strong> was carried out in bulk in a 5 mL vial sealed with a rubber septum with magnetic stirring. 0.062 g Novozym 435 was first introduced into a pre-dried vial and then subjected to an alternating vacuum-nitrogen purge cycle for three cycles. After that, 1.24 g <strong>[3041-16-5]PDO</strong> was injected into the vial through the rubber septum with a syringes. When the experiment was carried out in winter, usually P<strong>[3041-16-5]PDO</strong> is in a solid form due to its low melting point. So, a hair dryer was used to heat the syringe in order to maintain <strong>[3041-16-5]PDO</strong> with liquid state. When the polymerization was done in summer, there are no this trouble. There after, the vial was immersed in an oil bath at the predetermined temperature controlled within ±1C. After a predetermined polymerization time, the vials were rapidly put into an ice water. One fraction sample for 1H NMR analysis was dissolved in CDCl3 containing 1% tetramethylsilane and was then separated from the enzyme by filtration with a membrane filter (pore size = 0.45 m). All samples were synthesized in triplicate and then were tested by H NMR measurement. The resulting P<strong>[3041-16-5]PDO</strong> was purified by precipitation from the chloroform solution with methanol and dried in vacuum until constant weight.